JPWO2007029346A1 - Proton conductive hybrid material and catalyst layer for fuel cell using the same - Google Patents

Abstract

Provision of an organic-inorganic hybrid material capable of providing high proton conductivity in a wide range from low temperature to high temperature. Provided is a proton-conductive material having a small particle size, that is, a particle size that can reach the pores of primary particles such as carbon powder and the particle size is controlled. Provided are a fuel cell catalyst layer, a fuel cell electrolyte membrane, and a fuel cell containing these materials. A proton conductive hybrid material having proton conductive inorganic nanoparticles and a proton conductive polymer, wherein the proton conductive hybrid material has a Stokes particle size of 20 nm or less by a dynamic light scattering method. The above problems are solved by using materials.

Description

  The present invention relates to a proton conductive hybrid material having proton conductive inorganic nanoparticles and a proton conductive polymer, and relates to a proton conductive hybrid material having a controlled particle size. In particular, the present invention relates to a fuel cell catalyst layer in which a proton conductive hybrid material having a small particle size is controlled and incorporated in primary pores, and a method for producing the same.

  Since organic-inorganic nanocomposites can exhibit high conductivity and can achieve thermal stability at high temperatures, they have recently been used as proton conductors for practical application in polymer electrolyte membrane fuel cells (PEMFC). Much research has been done on the development and use of novel organic-inorganic nanocomposites.

  Considering the properties of proton conducting materials, polymer materials generally exhibit the desired conductivity under wet conditions, but are disadvantageous in that they degrade at high temperatures and preferably have high resistance values when not wet. is there. Inorganic conductors, on the other hand, are thermally and mechanically stable, but they are stiff and brittle and pure oxides do not exhibit high proton conductivity. However, as far as proton conductivity is concerned, their ability to retain water even at high temperatures is attractive. Thus, appropriate methods for improving the proton conductivity of these materials should be made.

  As common general knowledge in the scientific community, there is a growing need for new proton conductive materials that can exhibit considerable conductivity at high temperatures along with other properties. The synthesis of proton conducting inorganic-organic hybrid materials is one option to overcome the shortcomings in Nafion®, so it is believed that it can be used in PEMFCs operating at high temperatures. In hybrids, thermal stability is provided by inorganic materials, while polymers contribute to certain required properties such as flexibility and processability.

In addition, PEFC for automobiles requires continuous operation from -25 ° C. at the initial motion to 120 ° C. at the time of operation. Fluorine ionomers mainly used with Nafion (registered trademark) show good proton conductivity at low temperatures, but cannot be used at high temperatures due to a rapid decrease in proton conductivity and low heat resistance. In addition, fluorine ionomers are expensive to manufacture and use fluorine, which increases the environmental load. Alternative material SPES, which is a hydrocarbon ionomer, is affordable and has structure controllability, oxidation resistance and heat resistance, but water activity is required to exhibit high proton conductivity. (See Non-Patent Document 1). Therefore, hydrocarbon ionomers cannot maintain proton conductivity at high temperatures and normal pressures. In order to develop proton conductivity in a wide temperature range, it is necessary to construct a hybrid structure material. There have been many studies on modifying these materials with inorganic materials (heteropolyacid, hydrogen sulfate, inorganic solid proton conductor) that can maintain proton conductivity at high temperatures (see Non-Patent Document 2). Hydrated zirconia, one of the tetravalent metals in this case, can maintain proton conductivity at high temperatures. Hydrated zirconia is a precursor of ZrS and ZrP showing high proton conductivity. These studies are mainly used for ionomers as electrolyte membranes, and there are few studies as electrodes. In the electrode, as shown in FIG. 1, the catalyst layer comprising carbon as an electron transfer path, ionomer as a gas or proton transfer path, and a platinum catalyst as a power generation site has primary pores (20 to 40 nm) and aggregate size. It has a complicated structure such as secondary pores (40 nm). In the case of primary pores, the small pores prevent high molecular weight ionomers from penetrating and cannot form a proton pathway to the internal catalyst. Thus, the total utilization of the catalyst is only on the order of 20%. The size of the ionomer at the electrode is important. Contrary to the background of the electrode structure, the structural analysis of the electrode derived from the ionomer structure and the fuel cell performance have not yet been made.
Cotter, CJ EngineeringPlastics: A Handbook of Polyaryleters; Gordon & Breach: London, 1965. Li, Q. He, R. Jensen, JOBjerrum, NJ Chemistry of Material 15 (2003), 4896-4915.

A polymer electrolyte fuel cell (PEFC) using a highly active catalyst can be easily started at normal temperatures, produces small but large power, exhibits high conversion efficiency, and does not generate harmful gases such as NOx and SOx. PEFC is attracting attention as the next generation energy source. However, there are various problems in practical use, and it is necessary to optimize the PEFC system by considering characteristics for application. PEFC can be used as an energy source in mobile and stationary applications, as well as mobile applications. In particular, development of a novel electrolyte ionomer capable of maintaining high proton conductivity in a wide temperature range of −25 to 120 ° C. and low humidity is demanded for mobile applications such as automobiles.
For electrolyte ionomers used in membranes and electrodes that play an important role in creating electrical energy, it is difficult for a single material to satisfy such properties. Therefore, it is necessary to construct a hybrid material in which materials having new characteristics that cannot be provided by a single material are directly connected.

Therefore, an object of the present invention is to solve the above problems.
That is, an object of the present invention is to provide an organic-inorganic hybrid material that can provide high proton conductivity in a wide range from low temperature to high temperature.
In addition to the above object, an object of the present invention is to provide an organic-inorganic hybrid material that can provide high proton conductivity in a wide temperature range and low humidity.
Furthermore, the object of the present invention is not only in addition to the above object, but in addition to the above object, the particle diameter is small, that is, a particle diameter that can reach the pores of primary particles such as carbon powder. Is to provide a controlled proton conducting material.
Another object of the present invention is to provide a fuel cell catalyst layer and a fuel cell electrolyte membrane using the above materials, and a fuel cell using these.
Furthermore, the objective of this invention is providing the manufacturing method of said material, a catalyst layer, an electrolyte membrane, and a fuel cell.

More specifically, in this case, our aim is to develop a hybrid ionomer comprising an inorganic material, ie an organic material incorporating Zr (OH) ₂ (hydrated zirconia), ie SPES (sulfonated poly (arylene ether sulfone)). In the development of an electrode that operates with PEFC in a wide temperature range, the hybrid electrode is used to test the structural analysis of the electrode derived from the ionomer structure and the fuel cell performance.

The present inventor has found that the above-described problems can be solved by the following invention.
<1> A proton conductive hybrid material having proton conductive inorganic nanoparticles and a proton conductive polymer, wherein the Stokes particle size of the proton conductive hybrid material by a dynamic light scattering method is 20 nm or less, preferably 10 nm or less. The proton conductive hybrid material is more preferably 5 nm or less. Preferably, the proton conducting polymer is disposed in the vicinity of the proton conducting inorganic nanoparticles, and more preferably, the proton conducting polymer is disposed around the proton conducting inorganic nanoparticles.

<2> In the above item <1>, the proton conductive inorganic nanoparticles include zirconium compound, titanium compound, cerium compound, uranium compound, tin compound, vanadium compound, antimony compound, calcium hydroxyapatite, and hydrated calcium hydroxyapatite. It is at least one selected from the group consisting of, preferably a zirconium compound.
<3> In the above item <2>, the zirconium compound contains ZrO ₂ , ZrO ₂ .nH ₂ O, Zr (HPO ₄ ) ₂ , Zr (HPO ₄ ) ₂ .nH ₂ O, Zr (HSO ₃ ) ₂ , Zr. (HSO ₃ ) ₂ .nH ₂ O, Zr (O ₃ P—R ¹ —SO ₃ H) ₂ , Zr (O ₃ P—R ¹ —SO ₃ H) ₂ .nH ₂ O, Zr (O ₃ P— R ² —SO ₃ H) _2−x (O ₃ P—R ³ —COOH) _x , and Zr (O ₃ P—R ² —SO ₃ H) _2−x (O ₃ P—R ³ —COOH) _x NH ₂ O (wherein R ¹ , R ² , and R ³ each independently represent a divalent aromatic group, preferably R ¹ and R ² each independently represent a divalent aromatic group) R ³ represents an alkylene group) and is preferably at least one selected from the group consisting of

<4> In the above item <2>, the titanium compound includes TiO ₂ , TiO ₂ .nH ₂ O, Ti (HPO ₄ ) ₂ , Ti (HPO ₄ ) ₂ .nH ₂ O, Ti (HSO ₃ ) ₂ , and It may be at least one selected from the group consisting of Ti (HSO ₃ ) ₂ .nH ₂ O. In the above <2>, the cerium compound is at least one selected from the group consisting of CeO ₂ , CeO ₂ .nH ₂ O, Ce (HPO ₄ ) ₂ and Ce (HPO ₄ ) ₂ .nH ₂ O. Good. In the above <2>, the uranium compound is selected from the group consisting of H ₃ OUO ₄ PO ₄ , H ₃ OUO ₄ PO ₄ .nH ₂ O, H ₃ OUO ₂ AsO ₄ and H ₃ OUO ₂ AsO ₄ .nH ₂ O. It is good that it is at least one kind. In the above <2>, the tin compound may be SnO ₂ or SnO ₂ .nH ₂ O. In the above <2>, the vanadium compound may be V ₂ O ₅ or V ₂ O ₅ .nH ₂ O. In the above item <2>, antimony _{compounds, Sb 2 O 5, Sb 2} O 5 · nH 2 O, HSbO 3, HSbO 3 · nH 2 O, H 2 SbO 11, H 2 SbO 11 · nH 2 O, H x At least one selected from the group consisting of Sb _x P ₂ O ₃ and H _x Sb _x P ₂ O ₃ .nH ₂ O (wherein x is 1, 3 or 5 and n is 2 to 10). It is good to be. In the above <2>, calcium hydroxyapatite and hydrated calcium hydroxyapatite are Ca ₁₀ (PO ₄ ) X ₂ and Ca ₁₀ (PO ₄ ) X ₂ .nH ₂ O (wherein X is —OH and / or Or at least one selected from the group consisting of -F).

<5> In any one of the above items <1> to <4>, the proton conductive inorganic nanoparticles have a Stokes particle size of 20 nm or less, preferably 10 nm or less, more preferably 5 nm or less, by a dynamic light scattering method. Is good.
<6> In any one of the above items <1> to <5>, the proton conductive inorganic nanoparticles are on the order of 1 × 10 ⁻⁵ S / cm, preferably 1 × 10 ⁻³ S at a temperature of 20 to 150 ° C. Proton conductivity in the order of / cm, more preferably in the order of 1 × 10 ⁻² S / cm.
<7> In any one of the above items <1> to <6>, the proton conductive polymer is one or more of a hydrocarbon-based polymer group that can be dissolved in a polar organic solvent, preferably heat resistant. It may be one or more of the functional hydrocarbon-based polymer group.

<8> In the above <7>, the polar organic solvent is a group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide, preferably N, N-dimethylformamide, dimethyl sulfoxide and 1 -Preferably selected from the group consisting of methylpyrrolidone.
<9> In any one of the above items <1> to <8>, the proton conductive polymer may be one or more of a sulfonated hydrocarbon polymer group.
<10> In any one of the above items <1> to <9>, the proton conductive polymer may be chemically bonded to the proton conductive inorganic nanoparticles.
<11> In any one of the above items <1> to <10>, the proton conductive hybrid material is 10 ⁻³ S / cm to 1 S / cm at a temperature of −20 to 150 ° C. under low and high humidity. There should be.

  <12> A dispersion having a proton conductive hybrid material and a polar organic solvent, wherein the proton conductive hybrid material is selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide. Uniformly dispersed in the selected polar organic solvent, the proton conductive hybrid material has proton conductive inorganic nanoparticles and a proton conductive polymer, and the Stokes by the dynamic light scattering method of the proton conductive hybrid material. The above dispersion having a particle size of 20 nm or less, preferably 10 nm or less, more preferably 5 nm or less. Preferably, the proton conductive polymer is disposed in the vicinity of the proton conductive inorganic nanoparticles, and more preferably, the proton conductive polymer is disposed around the proton conductive inorganic nanoparticles.

<13> In the above item <12>, the proton conductive inorganic nanoparticles include zirconium compound, titanium compound, cerium compound, uranium compound, tin compound, vanadium compound, antimony compound, calcium hydroxyapatite, and hydrated calcium hydroxyapatite. It is at least one selected from the group consisting of, preferably a zirconium compound.
<14> In the above item <13>, the zirconium compound contains ZrO ₂ , ZrO ₂ .nH ₂ O, Zr (HPO ₄ ) ₂ , Zr (HPO ₄ ) ₂ .nH ₂ O, Zr (HSO ₃ ) ₂ , Zr (HSO ₃ ) ₂ · nH ₂ O, Zr (O ₃ P—R ¹ —SO ₃ H) ₂ , Zr (O ₃ P—R ¹ —SO ₃ H) ₂ .nH ₂ O, Zr (O ₃ P—R ^{2 _{-SO 3 H) 2-x (}} O 3 P-R 3 -COOH) x, and ^{_{Zr (O 3 P-R 2}} -SO 3 H) 2-x (O 3 P-R 3 -COOH) x · nH ₂ O (wherein R ¹ , R ² and R ³ each independently represents a divalent aromatic group, preferably R ¹ and R ² each independently represents a divalent aromatic group and R ³ is preferably at least one selected from the group consisting of an alkylene group.

<15> In the above item <13>, the titanium compound includes TiO ₂ , TiO ₂ .nH ₂ O, Ti (HPO ₄ ) ₂ , Ti (HPO ₄ ) ₂ .nH ₂ O, Ti (HSO ₃ ) ₂ , and It may be at least one selected from the group consisting of Ti (HSO ₃ ) ₂ .nH ₂ O. In the above <13>, the cerium compound is at least one selected from the group consisting of CeO ₂ , CeO ₂ .nH ₂ O, Ce (HPO ₄ ) ₂ and Ce (HPO ₄ ) ₂ .nH ₂ O. Good. In the above <13>, the uranium compound is selected from the group consisting of H ₃ OUO ₄ PO ₄ , H ₃ OUO ₄ PO ₄ .nH ₂ O, H ₃ OUO ₂ AsO ₄ and H ₃ OUO ₂ AsO ₄ .nH ₂ O. It is good that it is at least one kind. In the above <13>, the tin compound may be SnO ₂ or SnO ₂ .nH ₂ O. In the above <13>, the vanadium compound may be V ₂ O ₅ or V ₂ O ₅ .nH ₂ O. In the above item <13>, antimony _{compounds, Sb 2 O 5, Sb 2} O 5 · nH 2 O, HSbO 3, HSbO 3 · nH 2 O, H 2 SbO 11, H 2 SbO 11 · nH 2 O, H x At least one selected from the group consisting of Sb _x P ₂ O ₃ and H _x Sb _x P ₂ O ₃ .nH ₂ O (wherein x is 1, 3 or 5 and n is 2 to 10). It is good to be. In the above <13>, calcium hydroxyapatite and hydrated calcium hydroxyapatite are Ca ₁₀ (PO ₄ ) X ₂ and Ca ₁₀ (PO ₄ ) X ₂ .nH ₂ O (wherein X is —OH and / or Or at least one selected from the group consisting of -F).
<16> In any one of the above items <12> to <15>, the proton conductive inorganic nanoparticles have a Stokes particle size of 20 nm or less, preferably 10 nm or less, more preferably 5 nm or less, by a dynamic light scattering method. Is good.

<17> In any one of the above items <12> to <16>, the proton-conductive inorganic nanoparticles are on the order of 1 × 10 ⁻⁵ S / cm, preferably 1 × 10 ⁻³ S at a temperature of 20 to 150 ° C. Proton conductivity in the order of / cm, more preferably in the order of 1 × 10 ⁻² S / cm.
<18> In any one of the above items <12> to <17>, the proton conductive polymer may be one or more of a hydrocarbon-based polymer group that can be dissolved in the polar organic solvent, preferably It may be one or more of the group of heat resistant hydrocarbon polymers.

<19> In any one of the above items <12> to <18>, the polar organic solvent may be selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide and 1-methylpyrrolidone.
<20> In any one of the above items <12> to <19>, the proton conductive polymer may be one or more of a sulfonated hydrocarbon polymer group.
<21> In any one of the above items <12> to <20>, the proton conductive polymer may be chemically bonded to the proton conductive inorganic nanoparticles.

<22> A method for producing a dispersion having a proton conductive hybrid material and a polar organic solvent, the method comprising:
Dissolving a proton conductive polymer in a first polar organic solvent selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide to obtain a polymer solution;
Proton conductivity to a second polar organic solvent selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide which is the same as or different from the first polar organic solvent Dispersing inorganic nanoparticles to obtain a nanoparticle dispersion; and pouring the polymer solution into the nanoparticle dispersion, or pouring the nanoparticle dispersion into the polymer solution, and the organic solvent and proton conductivity. Obtaining the dispersion with a hybrid material,
The material has the proton conductive inorganic nanoparticles and the proton conductive polymer, and the proton conductive hybrid material has a Stokes particle size of 20 nm or less, preferably 10 nm or less, more preferably 5 nm, by a dynamic light scattering method. The method as described below. Preferably, the proton conductive polymer is disposed in the vicinity of the proton conductive inorganic nanoparticles, and more preferably, the proton conductive polymer is disposed around the proton conductive inorganic nanoparticles.

<23> In the above item <22>, in addition to the dispersion obtained from the poor organic solvent for the proton conductive polymer, the method further includes a step of obtaining a dispersion having a proton conductive hybrid material having a smaller Stokes particle size. Is good.
<24> In the above item <23>, the poor organic solvent may be selected from the group consisting of methanol, ethanol, isopropanol, butanol, and hexane, preferably isopropanol.

<25> In any one of the above items <22> to <24>, the proton-conductive inorganic nanoparticles include a zirconium compound, a titanium compound, a cerium compound, a uranium compound, a tin compound, a vanadium compound, an antimony compound, and calcium hydroxyapatite. And at least one selected from the group consisting of hydrated calcium / hydroxyapatite, preferably a zirconium compound.
<26> In the above item <25>, the zirconium compound includes ZrO ₂ , ZrO ₂ .nH ₂ O, Zr (HPO ₄ ) ₂ , Zr (HPO ₄ ) ₂ .nH ₂ O, Zr (HSO ₃ ) ₂ , Zr (HSO ₃ ) ₂ · nH ₂ O, Zr (O ₃ P—R ¹ —SO ₃ H) ₂ , Zr (O ₃ P—R ¹ —SO ₃ H) ₂ .nH ₂ O, Zr (O ₃ P—R ^{2 _{-SO 3 H) 2-x (}} O 3 P-R 3 -COOH) x, and ^{_{Zr (O 3 P-R 2}} -SO 3 H) 2-x (O 3 P-R 3 -COOH) x · nH ₂ O (wherein R ¹ , R ² and R ³ each independently represents a divalent aromatic group, preferably R ¹ and R ² each independently represents a divalent aromatic group and R ³ is preferably at least one selected from the group consisting of an alkylene group.

<27> In the above <25>, the titanium compound includes TiO ₂ , TiO ₂ .nH ₂ O, Ti (HPO ₄ ) ₂ , Ti (HPO ₄ ) ₂ .nH ₂ O, Ti (HSO ₃ ) ₂ , and It may be at least one selected from the group consisting of Ti (HSO ₃ ) ₂ .nH ₂ O. In the above <25>, the cerium compound is at least one selected from the group consisting of CeO ₂ , CeO ₂ .nH ₂ O, Ce (HPO ₄ ) ₂ and Ce (HPO ₄ ) ₂ .nH ₂ O. Good. In the above item <25>, uranium _compounds, selected from _{H 3 OUO 4 PO 4, H} 3 OUO 4 PO 4 · nH 2 O, H 3 OUO 2 AsO 4 and _{H 3 OUO 2 AsO 4 · nH} 2 O consisting of the group It is good that it is at least one kind. In the above <25>, the tin compound may be SnO ₂ or SnO ₂ .nH ₂ O. In the above <25>, the vanadium compound may be V ₂ O ₅ or V ₂ O ₅ .nH ₂ O. In the above item <25>, antimony _{compounds, Sb 2 O 5, Sb 2} O 5 · nH 2 O, HSbO 3, HSbO 3 · nH 2 O, H 2 SbO 11, H 2 SbO 11 · nH 2 O, H x At least one selected from the group consisting of Sb _x P ₂ O ₃ and H _x Sb _x P ₂ O ₃ .nH ₂ O (wherein x is 1, 3 or 5 and n is 2 to 10). It is good to be. In the above <25>, calcium hydroxyapatite and hydrated calcium hydroxyapatite are Ca ₁₀ (PO ₄ ) X ₂ and Ca ₁₀ (PO ₄ ) X ₂ .nH ₂ O (wherein X is —OH and / or Or at least one selected from the group consisting of -F).

<28> In any one of the above items <22> to <27>, the proton conductive inorganic nanoparticles have a Stokes particle size of 20 nm or less, preferably 10 nm or less, more preferably 5 nm or less, by a dynamic light scattering method. Is good.
<29> In any one of the above items <22> to <28>, the proton-conductive inorganic nanoparticles are on the order of 1 × 10 ⁻⁵ S / cm, preferably 1 × 10 ⁻³ S at a temperature of 20 to 150 ° C. Proton conductivity in the order of / cm, more preferably in the order of 1 × 10 ⁻² S / cm.
<30> In any one of the above items <22> to <29>, the proton conductive polymer may be one or more of a hydrocarbon-based polymer group that can be dissolved in the polar organic solvent, preferably It may be one or more of the group of heat resistant hydrocarbon polymers.

<31> In any one of the above items <22> to <30>, the first and / or second polar organic solvent is selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide and 1-methylpyrrolidone. It is good.
<32> In any one of the above items <22> to <31>, the proton conductive polymer may be one or more of a sulfonated hydrocarbon polymer group.
<33> In any one of the above items <22> to <32>, in the step of pouring the polymer solution into the nanoparticle dispersion or the step of pouring the nanoparticle dispersion into the polymer solution, the proton conductive polymer is the proton conductive inorganic It is preferable that a part of or all of the proton conductive polymer reacts with the nanoparticles and chemically bonds with the proton conductive inorganic nanoparticles.

<34> A method for producing a proton conductive hybrid material having a proton conductive polymer and proton conductive inorganic nanoparticles, the method comprising:
Dissolving a proton conductive polymer in a first polar organic solvent selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide to obtain a polymer solution;
Proton conductivity in a second polar organic solvent selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide which is the same as or different from the first polar organic solvent Dispersing inorganic nanoparticles to obtain a nanoparticle dispersion; and pouring the polymer solution into the nanoparticle dispersion, or pouring the nanoparticle dispersion into the polymer solution, and the organic solvent and proton conductivity. Obtaining the dispersion having a hybrid material; and removing the first and second polar organic solvents from the obtained dispersion to obtain the proton conductive hybrid material;
The above method, wherein the proton conductive hybrid material has a Stokes particle size of 20 nm or less, preferably 10 nm or less, more preferably 5 nm or less by a dynamic light scattering method. Preferably, the proton conductive polymer is disposed in the vicinity of the proton conductive inorganic nanoparticles, and more preferably, the proton conductive polymer is disposed around the proton conductive inorganic nanoparticles.

<35> In the above item <34>, in addition to the dispersion obtained from the poor organic solvent for the proton conductive polymer, the method further includes a step of obtaining a dispersion having a proton conductive hybrid material having a smaller Stokes particle size. Is good.
<36> In the above item <35>, the poor organic solvent may be selected from the group consisting of methanol, ethanol, isopropanol, butanol and hexane, and preferably is isopropanol.

<37> In any one of the above items <33> to <36>, the proton conductive inorganic nanoparticles include a zirconium compound, a titanium compound, a cerium compound, a uranium compound, a tin compound, a vanadium compound, an antimony compound, and calcium hydroxyapatite. And at least one selected from the group consisting of hydrated calcium / hydroxyapatite, preferably a zirconium compound.
<38> In the above <37>, the zirconium compound contains ZrO ₂ , ZrO ₂ .nH ₂ O, Zr (HPO ₄ ) ₂ , Zr (HPO ₄ ) ₂ .nH ₂ O, Zr (HSO ₃ ) ₂ , Zr (HSO ₃ ) ₂ · nH ₂ O, Zr (O ₃ P—R ¹ —SO ₃ H) ₂ , Zr (O ₃ P—R ¹ —SO ₃ H) ₂ .nH ₂ O, Zr (O ₃ P—R ^{2 _{-SO 3 H) 2-x (}} O 3 P-R 3 -COOH) x, and ^{_{Zr (O 3 P-R 2}} -SO 3 H) 2-x (O 3 P-R 3 -COOH) x · nH ₂ O (wherein R ¹ , R ² and R ³ each independently represents a divalent aromatic group, preferably R ¹ and R ² each independently represents a divalent aromatic group and R ³ is preferably at least one selected from the group consisting of an alkylene group.

<39> In the above <37>, the titanium compound includes TiO ₂ , TiO ₂ .nH ₂ O, Ti (HPO ₄ ) ₂ , Ti (HPO ₄ ) ₂ .nH ₂ O, Ti (HSO ₃ ) ₂ , and It may be at least one selected from the group consisting of Ti (HSO ₃ ) ₂ .nH ₂ O. In the above <37>, the cerium compound is at least one selected from the group consisting of CeO ₂ , CeO ₂ .nH ₂ O, Ce (HPO ₄ ) ₂ and Ce (HPO ₄ ) ₂ .nH ₂ O. Good. In the above <37>, the uranium compound is selected from the group consisting of H ₃ OUO ₄ PO ₄ , H ₃ OUO ₄ PO ₄ .nH ₂ O, H ₃ OUO ₂ AsO ₄ and H ₃ OUO ₂ AsO ₄ .nH ₂ O. It is good that it is at least one kind. In the above <37>, the tin compound may be SnO ₂ or SnO ₂ · nH ₂ O. In the above <37>, the vanadium compound may be V ₂ O ₅ or V ₂ O ₅ .nH ₂ O. In the above item <37>, antimony _{compounds, Sb 2 O 5, Sb 2} O 5 · nH 2 O, HSbO 3, HSbO 3 · nH 2 O, H 2 SbO 11, H 2 SbO 11 · nH 2 O, H x At least one selected from the group consisting of Sb _x P ₂ O ₃ and H _x Sb _x P ₂ O ₃ .nH ₂ O (wherein x is 1, 3 or 5 and n is 2 to 10). It is good to be. In the above <37>, calcium hydroxyapatite and hydrated calcium hydroxyapatite are Ca ₁₀ (PO ₄ ) X ₂ and Ca ₁₀ (PO ₄ ) X ₂ .nH ₂ O (wherein X is —OH and / or Or at least one selected from the group consisting of -F).

<40> In any one of the above items <34> to <39>, the proton conductive inorganic nanoparticles have a Stokes particle size of 20 nm or less, preferably 10 nm or less, more preferably 5 nm or less, by a dynamic light scattering method. Is good.
<41> In any one of the above items <34> to <40>, the proton conductive inorganic nanoparticles are on the order of 1 × 10 ⁻⁵ S / cm, preferably 1 × 10 ⁻³ S at a temperature of 20 to 150 ° C. Proton conductivity in the order of / cm, more preferably in the order of 1 × 10 ⁻² S / cm.
<42> In any one of the above items <34> to <41>, the proton conductive polymer may be one or more of a hydrocarbon-based polymer group that can be dissolved in the polar organic solvent, preferably It may be one or more of the group of heat resistant hydrocarbon polymers.

<43> In any one of the above items <34> to <42>, the first and / or second polar organic solvent is selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide and 1-methylpyrrolidone. It is good.
<44> In any one of the above items <34> to <43>, the proton conductive polymer may be one or more of a sulfonated hydrocarbon polymer group.
<45> In any one of the above <34> to <44>, in the step of pouring the polymer solution into the nanoparticle dispersion or the step of pouring the nanoparticle dispersion into the polymer solution, the proton conductive polymer is the proton conductive inorganic It is preferable that a part of or all of the proton conducting polymer reacts with the nanoparticles and chemically bonds with the proton conducting inorganic nanoparticles.

<46> A fuel cell catalyst layer comprising an electron conductor, a catalyst, and a proton conductive hybrid material,
The proton conductive hybrid material has proton conductive inorganic nanoparticles and a proton conductive polymer;
The catalyst layer, wherein the proton conductive hybrid material has a Stokes particle size of 20 nm or less, preferably 10 nm or less, and more preferably 5 nm or less by a dynamic light scattering method. Preferably, the proton conducting polymer is disposed in the vicinity of the proton conducting inorganic nanoparticles, and more preferably, the proton conducting polymer is disposed around the proton conducting inorganic nanoparticles.

<47> In the above <46>, the catalyst layer is arranged such that the catalyst is supported on the surface of the electron conductor, and the proton conductive hybrid material is arranged in the vicinity of a position where the catalyst is arranged. It is good to be configured.
<48> In the above <46> or <47>, the proton conductive hybrid material may be physically and / or chemically bonded to the electron conductor.
<49> In any one of the above items <46> to <48>, the electron conductor may be a carbon-based porous electron conductor or a metal-based porous electron conductor, preferably a carbon-based porous electron. It should be a conductor.

<50> In the above item <49>, the carbon-based porous electron conductor may be selected from the group consisting of carbon black, acetylene black, graphite, carbon fiber, carbon nanotube, fullerene, activated carbon, and glass carbon.
<51> In any one of the above items <46> to <50>, the electron conductor may have a particle size of 300 nm or less, preferably 100 nm or less, more preferably 30 nm or less.
<52> In any one of the above items <46> to <51>, the catalyst may be selected from the group consisting of a noble metal catalyst group and an organic catalyst group. Examples of the noble metal catalyst include, but are not limited to, Pt and Pt—Ru.

<53> In any one of the above items <46> to <52>, the catalyst may have a particle size of 30 nm or less, preferably 10 nm or less, more preferably 3 nm or less.
<54> In any one of the above items <46> to <53>, the proton conductive inorganic nanoparticles include a zirconium compound, a titanium compound, a cerium compound, a uranium compound, a tin compound, a vanadium compound, an antimony compound, and calcium hydroxyapatite. And at least one selected from the group consisting of hydrated calcium / hydroxyapatite, preferably a zirconium compound.
<55> In the above item <54>, the zirconium compound includes ZrO ₂ , ZrO ₂ .nH ₂ O, Zr (HPO ₄ ) ₂ , Zr (HPO ₄ ) ₂ .nH ₂ O, Zr (HSO ₃ ) ₂ , Zr (HSO ₃ ) ₂ · nH ₂ O, Zr (O ₃ P—R ¹ —SO ₃ H) ₂ , Zr (O ₃ P—R ¹ —SO ₃ H) ₂ .nH ₂ O, Zr (O ₃ P—R ^{2 _{-SO 3 H) 2-x (}} O 3 P-R 3 -COOH) x, and ^{_{Zr (O 3 P-R 2}} -SO 3 H) 2-x (O 3 P-R 3 -COOH) x · nH ₂ O (wherein R ¹ , R ² and R ³ each independently represents a divalent aromatic group, preferably R ¹ and R ² each independently represents a divalent aromatic group and R ³ is preferably at least one selected from the group consisting of an alkylene group.

<56> In the above <54>, the titanium compound includes TiO ₂ , TiO ₂ · nH ₂ O, Ti (HPO ₄ ) ₂ , Ti (HPO ₄ ) ₂ · nH ₂ O, Ti (HSO ₃ ) ₂ , and It may be at least one selected from the group consisting of Ti (HSO ₃ ) ₂ .nH ₂ O. In the above <54>, the cerium compound is at least one selected from the group consisting of CeO ₂ , CeO ₂ .nH ₂ O, Ce (HPO ₄ ) ₂ and Ce (HPO ₄ ) ₂ .nH ₂ O. Good. In the above <54>, the uranium compound is selected from the group consisting of H ₃ OUO ₄ PO ₄ , H ₃ OUO ₄ PO ₄ .nH ₂ O, H ₃ OUO ₂ AsO ₄ and H ₃ OUO ₂ AsO ₄ .nH ₂ O. It is good that it is at least one kind. In the above <54>, the tin compound may be SnO ₂ or SnO ₂ .nH ₂ O. In the above <54>, the vanadium compound may be V ₂ O ₅ or V ₂ O ₅ .nH ₂ O. In the above item <54>, antimony _{compounds, Sb 2 O 5, Sb 2} O 5 · nH 2 O, HSbO 3, HSbO 3 · nH 2 O, H 2 SbO 11, H 2 SbO 11 · nH 2 O, H x At least one selected from the group consisting of Sb _x P ₂ O ₃ and H _x Sb _x P ₂ O ₃ .nH ₂ O (wherein x is 1, 3 or 5 and n is 2 to 10). It is good to be. In the above <54>, calcium hydroxyapatite and hydrated calcium hydroxyapatite are Ca ₁₀ (PO ₄ ) X ₂ and Ca ₁₀ (PO ₄ ) X ₂ .nH ₂ O (wherein X is —OH and / or Or at least one selected from the group consisting of -F).

<57> In any one of the above items <46> to <56>, the proton-conductive inorganic nanoparticles have a Stokes particle size of 20 nm or less, preferably 10 nm or less, more preferably 5 nm or less by a dynamic light scattering method. Is good.
<58> In any one of the above <46> to <57>, the proton-conductive inorganic nanoparticles are on the order of 1 × 10 ⁻⁵ S / cm, preferably 1 × 10 ⁻³ S at a temperature of 20 to 150 ° C. Proton conductivity in the order of / cm, more preferably in the order of 1 × 10 ⁻² S / cm.
<59> In any one of the above items <46> to <58>, the proton conductive polymer is one or more of a hydrocarbon-based polymer group that can be dissolved in a polar organic solvent, preferably heat resistant. It may be one or more of the functional hydrocarbon-based polymer group.

<60> In the above item <59>, the polar organic solvent is a group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide, preferably N, N-dimethylformamide, dimethyl sulfoxide and 1 -Preferably selected from the group consisting of methylpyrrolidone.
<61> In any one of the above items <46> to <60>, the proton conductive polymer may be one or more of a sulfonated hydrocarbon polymer group.
<62> In any one of the above items <46> to <61>, the proton conductive polymer may be chemically bonded to the proton conductive inorganic nanoparticles.

<63> A method for producing a fuel cell catalyst layer comprising an electron conductor, a catalyst, and a proton conductive hybrid material, the method comprising:
a) supporting the catalyst on the electron conductor;
b) preparing a proton conductive hybrid material dispersion in which the proton conductive hybrid material is dispersed in a polar organic solvent;
c) mixing the dispersion with the electronic conductor carrying the catalyst to obtain a mixture; and d) applying the mixture to a fuel cell diffusion layer to obtain a fuel cell catalyst layer. Having
The proton conductive hybrid material has proton conductive inorganic nanoparticles and a proton conductive polymer;
The above method, wherein the proton conductive hybrid material has a Stokes particle size of 20 nm or less, preferably 10 nm or less, more preferably 5 nm or less by a dynamic light scattering method. Preferably, the proton conducting polymer is disposed in the vicinity of the proton conducting inorganic nanoparticles, and more preferably, the proton conducting polymer is disposed around the proton conducting inorganic nanoparticles.

<64> In the above <63>, the method may further include a step of mixing a binder with the mixture at the time of the step c) or after the step c) and before the step d).
<65> In the above item <63> or <64>, the method may further include a step of adjusting the viscosity of the mixture by removing the solvent in the mixture.
<66> In any one of the above items <63> to <65>, in the step b), the proton conductive polymer is made of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide. A step of obtaining a polymer solution by dissolving in a first polar organic solvent selected from:
Proton conductivity in a second polar organic solvent selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide which is the same as or different from the first polar organic solvent It is preferable to further include a step of dispersing inorganic nanoparticles to obtain a nanoparticle dispersion; and a step of pouring the polymer solution into the nanoparticle dispersion or a step of pouring the nanoparticle dispersion into the polymer solution.

<67> In the above <66>, in the step b), in addition to the dispersion obtained from the poor organic solvent for the proton conductive polymer, a dispersion having a proton conductive hybrid material having a smaller Stokes particle size is obtained. It is good to have the process of obtaining.
<68> In the above <67>, the poor organic solvent may be selected from the group consisting of methanol, ethanol, isopropanol, butanol and hexane, and preferably isopropanol.
<69> In step b) in any of the above <63> to <68>, the proton conductive polymer reacts with the proton conductive inorganic nanoparticles, and a part or all of one end of the proton conductive polymer is It may be chemically bonded to the proton conductive inorganic nanoparticles.

<70> In any one of the above items <63> to <69>, in the catalyst layer, the catalyst is supported on the surface of the electron conductor, and the proton conductive hybrid material is a position where the catalyst is disposed. It is good to be arranged so that it is arranged in the vicinity.
<71> In any one of the above items <63> to <70>, the proton conductive hybrid material may be physically and / or chemically bonded to the electron conductor.
<72> In any one of the above items <63> to <71>, the electron conductor may be a carbon-based porous electron conductor or a metal-based porous electron conductor, preferably a carbon-based porous electron. It should be a conductor.

<73> In the above <72>, the carbon-based porous electron conductor may be selected from the group consisting of carbon black, acetylene black, graphite, carbon fiber, carbon nanotube, fullerene, activated carbon, and glass carbon.
<74> In any one of the above items <63> to <73>, the electron conductor may have a particle size of 300 nm or less, preferably 100 nm or less, more preferably 30 nm or less.
<75> In any one of the above items <63> to <74>, the catalyst may be selected from the group consisting of a noble metal catalyst group and an organic catalyst group. Examples of the noble metal catalyst include, but are not limited to, Pt and Pt—Ru.

<76> In any one of the above items <63> to <75>, the catalyst may have a particle size of 30 nm or less, preferably 10 nm or less, more preferably 3 nm or less.
<77> In any one of the above items <63> to <76>, the proton-conductive inorganic nanoparticles include a zirconium compound, a titanium compound, a cerium compound, a uranium compound, a tin compound, a vanadium compound, an antimony compound, and calcium hydroxyapatite. And at least one selected from the group consisting of hydrated calcium / hydroxyapatite, preferably a zirconium compound.
<78> In the above <77>, the zirconium compound contains ZrO ₂ , ZrO ₂ .nH ₂ O, Zr (HPO ₄ ) ₂ , Zr (HPO ₄ ) ₂ .nH ₂ O, Zr (HSO ₃ ) ₂ , Zr (HSO ₃ ) ₂ · nH ₂ O, Zr (O ₃ P—R ¹ —SO ₃ H) ₂ , Zr (O ₃ P—R ¹ —SO ₃ H) ₂ .nH ₂ O, Zr (O ₃ P—R ^{2 _{-SO 3 H) 2-x (}} O 3 P-R 3 -COOH) x, and ^{_{Zr (O 3 P-R 2}} -SO 3 H) 2-x (O 3 P-R 3 -COOH) x · nH ₂ O (wherein R ¹ , R ² and R ³ each independently represents a divalent aromatic group, preferably R ¹ and R ² each independently represents a divalent aromatic group and R ³ is preferably at least one selected from the group consisting of an alkylene group.

<79> In the above <77>, the titanium compound includes TiO ₂ , TiO ₂ .nH ₂ O, Ti (HPO ₄ ) ₂ , Ti (HPO ₄ ) ₂ .nH ₂ O, Ti (HSO ₃ ) ₂ , and It may be at least one selected from the group consisting of Ti (HSO ₃ ) ₂ .nH ₂ O. In the above <77>, the cerium compound is at least one selected from the group consisting of CeO ₂ , CeO ₂ .nH ₂ O, Ce (HPO ₄ ) ₂ and Ce (HPO ₄ ) ₂ .nH ₂ O. Good. In the above <77>, the uranium compound is selected from the group consisting of H ₃ OUO ₄ PO ₄ , H ₃ OUO ₄ PO ₄ .nH ₂ O, H ₃ OUO ₂ AsO ₄ and H ₃ OUO ₂ AsO ₄ .nH ₂ O. It is good that it is at least one kind. In the above <77>, the tin compound may be SnO ₂ or SnO ₂ .nH ₂ O. In the above <77>, the vanadium compound may be V ₂ O ₅ or V ₂ O ₅ .nH ₂ O. In the above item <77>, antimony _{compounds, Sb 2 O 5, Sb 2} O 5 · nH 2 O, HSbO 3, HSbO 3 · nH 2 O, H 2 SbO 11, H 2 SbO 11 · nH 2 O, H x At least one selected from the group consisting of Sb _x P ₂ O ₃ and H _x Sb _x P ₂ O ₃ .nH ₂ O (wherein x is 1, 3 or 5 and n is 2 to 10). It is good to be. In the above <77>, calcium hydroxyapatite and hydrated calcium hydroxyapatite are Ca ₁₀ (PO ₄ ) X ₂ and Ca ₁₀ (PO ₄ ) X ₂ .nH ₂ O (wherein X is —OH and / or Or at least one selected from the group consisting of -F).

<80> In any one of the above items <63> to <79>, the proton-conductive inorganic nanoparticles have a Stokes particle size of 20 nm or less, preferably 10 nm or less, more preferably 5 nm or less by a dynamic light scattering method. Is good.
<81> In any one of the above items <63> to <80>, the proton conductive inorganic nanoparticles are on the order of 1 × 10 ⁻⁵ S / cm, preferably 1 × 10 ⁻³ S at a temperature of 20 to 150 ° C. Proton conductivity in the order of / cm, more preferably in the order of 1 × 10 ⁻² S / cm.
<82> In any one of the above items <63> to <81>, the proton conductive polymer is one or more of a hydrocarbon-based polymer group that can be dissolved in a polar organic solvent, preferably heat resistant. It may be one or more of the functional hydrocarbon-based polymer group.

<83> In any one of the above items <66> to <82>, the polar organic solvent is a group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide, preferably N, N— It may be selected from the group consisting of dimethylformamide, dimethyl sulfoxide and 1-methylpyrrolidone.
<84> In any one of the above items <66> to <83>, the proton conductive polymer may be one or more of a sulfonated hydrocarbon polymer group.

  <85> An electrolyte membrane for a fuel cell having a proton-conductive hybrid material, the proton-conductive hybrid material having proton-conductive inorganic nanoparticles and a proton-conductive polymer. The above electrolyte membrane having a Stokes particle size of 20 nm or less, preferably 10 nm or less, more preferably 5 nm or less by a dynamic light scattering method. Preferably, the proton conducting polymer is disposed in the vicinity of the proton conducting inorganic nanoparticles, and more preferably, the proton conducting polymer is disposed around the proton conducting inorganic nanoparticles.

<86> In the above item <85>, the electrolyte membrane may have a base material, and the proton conductive hybrid material may be chemically and / or physically bonded to the base material.
<87> In the above <86>, the substrate may be selected from the group consisting of a porous polymer and a porous ceramic. Examples of the porous polymer include polyimide and polyethylene. Examples of the porous ceramic include alumina, silica, zirconia, and titania.
<88> In any one of the above items <85> to <87>, the proton conductive inorganic nanoparticles include a zirconium compound, a titanium compound, a cerium compound, a uranium compound, a tin compound, a vanadium compound, an antimony compound, and calcium hydroxyapatite. And at least one selected from the group consisting of hydrated calcium / hydroxyapatite, preferably a zirconium compound.

<89> In the above <88>, the zirconium compound includes ZrO ₂ , ZrO ₂ .nH ₂ O, Zr (HPO ₄ ) ₂ , Zr (HPO ₄ ) ₂ .nH ₂ O, Zr (HSO ₃ ) ₂ , Zr (HSO ₃ ) ₂ · nH ₂ O, Zr (O ₃ P—R ¹ —SO ₃ H) ₂ , Zr (O ₃ P—R ¹ —SO ₃ H) ₂ .nH ₂ O, Zr (O ₃ P—R ^{2 _{-SO 3 H) 2-x (}} O 3 P-R 3 -COOH) x, and ^{_{Zr (O 3 P-R 2}} -SO 3 H) 2-x (O 3 P-R 3 -COOH) x · nH ₂ O (wherein R ¹ , R ² and R ³ each independently represents a divalent aromatic group, preferably R ¹ and R ² each independently represents a divalent aromatic group and R ³ is preferably at least one selected from the group consisting of an alkylene group.

<90> In the above <88>, the titanium compound includes TiO ₂ , TiO ₂ .nH ₂ O, Ti (HPO ₄ ) ₂ , Ti (HPO ₄ ) ₂ .nH ₂ O, Ti (HSO ₃ ) ₂ , and It may be at least one selected from the group consisting of Ti (HSO ₃ ) ₂ .nH ₂ O. In the above <88>, the cerium compound is at least one selected from the group consisting of CeO ₂ , CeO ₂ .nH ₂ O, Ce (HPO ₄ ) ₂ and Ce (HPO ₄ ) ₂ .nH ₂ O. Good. In the above <88>, the uranium compound is selected from the group consisting of H ₃ OUO ₄ PO ₄ , H ₃ OUO ₄ PO ₄ .nH ₂ O, H ₃ OUO ₂ AsO ₄ and H ₃ OUO ₂ AsO ₄ .nH ₂ O. It is good that it is at least one kind. In the above <88>, the tin compound may be SnO ₂ or SnO ₂ .nH ₂ O. In the above <88>, the vanadium compound may be V ₂ O ₅ or V ₂ O ₅ .nH ₂ O. In the above item <88>, antimony _{compounds, Sb 2 O 5, Sb 2} O 5 · nH 2 O, HSbO 3, HSbO 3 · nH 2 O, H 2 SbO 11, H 2 SbO 11 · nH 2 O, H x At least one selected from the group consisting of Sb _x P ₂ O ₃ and H _x Sb _x P ₂ O ₃ .nH ₂ O (wherein x is 1, 3 or 5 and n is 2 to 10). It is good to be. In the above <88>, calcium hydroxyapatite and hydrated calcium hydroxyapatite are Ca ₁₀ (PO ₄ ) X ₂ and Ca ₁₀ (PO ₄ ) X ₂ .nH ₂ O (wherein X is —OH and / or Or at least one selected from the group consisting of -F).

<91> In any one of the above items <85> to <90>, the proton conductive inorganic nanoparticles have a Stokes particle size of 20 nm or less, preferably 10 nm or less, more preferably 5 nm or less, by a dynamic light scattering method. Is good.
<92> In any one of the above items <85> to <91>, the proton conductive inorganic nanoparticles are on the order of 1 × 10 ⁻⁵ S / cm, preferably 1 × 10 ⁻³ S at a temperature of 20 to 150 ° C. Proton conductivity in the order of / cm, more preferably in the order of 1 × 10 ⁻² S / cm.
<93> In any one of the above items <85> to <92>, the proton conductive polymer is one or more of a hydrocarbon-based polymer group that can be dissolved in a polar organic solvent, preferably heat resistant. It may be one or more of the functional hydrocarbon polymer group.

  <94> In the above <93>, the polar organic solvent is a group consisting of N, N-dimethylformamide, dimethylsulfoxide, 1-methylpyrrolidone and N-methylacetamide, preferably N, N-dimethylformamide, dimethylsulfoxide and 1 -Preferably selected from the group consisting of methylpyrrolidone.

<95> In any one of the above items <85> to <94>, the proton conductive polymer may be one or more of a sulfonated hydrocarbon polymer group.
<96> In any one of the above items <85> to <95>, the proton conductive polymer may be chemically bonded to the proton conductive inorganic nanoparticles.
<97> In any one of the above items <85> to <96>, the electrolyte membrane for a fuel cell is 10 ⁻² S / cm to 5 S / cm at a temperature of −20 to 150 ° C. under low and high humidity. There should be.

<98> A method for producing an electrolyte membrane for a fuel cell comprising a porous substrate and a proton conductive hybrid material, the method comprising:
x) preparing a proton conductive hybrid material dispersion in which the proton conductive hybrid material is dispersed in a polar organic solvent; and y) applying the dispersion to the holes of the substrate or the holes and surface of the substrate. And obtaining a fuel cell electrolyte membrane,
The proton conductive hybrid material has proton conductive inorganic nanoparticles and a proton conductive polymer;
The above method, wherein the proton conductive hybrid material has a Stokes particle size of 20 nm or less, preferably 10 nm or less, more preferably 5 nm or less by a dynamic light scattering method. Preferably, the proton conducting polymer is disposed in the vicinity of the proton conducting inorganic nanoparticles, and more preferably, the proton conducting polymer is disposed around the proton conducting inorganic nanoparticles.

<99> In the above <98>, the step x)
Dissolving the proton conductive polymer in a first polar organic solvent selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide to obtain a polymer solution;
Proton conductivity in a second polar organic solvent selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide which is the same as or different from the first polar organic solvent It is preferable to further include a step of dispersing inorganic nanoparticles to obtain a nanoparticle dispersion; and a step of pouring the polymer solution into the nanoparticle dispersion or a step of pouring the nanoparticle dispersion into the polymer solution.

<100> In the above <99>, in the step b), a dispersion having a proton conductive hybrid material having a smaller Stokes particle size in addition to a poor organic solvent for the proton conductive polymer in addition to the obtained dispersion It is good to have the process of obtaining.
<101> In the above <100>, the poor organic solvent may be selected from the group consisting of methanol, ethanol, isopropanol, butanol and hexane, preferably isopropanol.
<102> In step x) in any one of the above <98> to <101>, the proton conductive polymer reacts with the proton conductive inorganic nanoparticles, and a part or all of one end of the proton conductive polymer is It may be chemically bonded to the proton conductive inorganic nanoparticles.

<103> In step y) in any one of the above <98> to <102>, the proton conductive polymer reacts with the pores and / or the surface of the base material, and a part or all of the proton conductive polymer One end is preferably chemically bonded to the substrate.
<104> In any one of the above items <98> to <103>, the base material may be selected from the group consisting of a porous polymer and a porous ceramic. Examples of the porous polymer include polyimide and polyethylene. Examples of the porous ceramic include alumina, silica, zirconia, and titania.
<105> In any one of the above items <98> to <104>, the proton conductive inorganic nanoparticles include a zirconium compound, a titanium compound, a cerium compound, a uranium compound, a tin compound, a vanadium compound, an antimony compound, and calcium hydroxyapatite. And at least one selected from the group consisting of hydrated calcium / hydroxyapatite, preferably a zirconium compound.

<106> In the above <105>, the zirconium compound contains ZrO ₂ , ZrO ₂ .nH ₂ O, Zr (HPO ₄ ) ₂ , Zr (HPO ₄ ) ₂ .nH ₂ O, Zr (HSO ₃ ) ₂ , Zr (HSO ₃ ) ₂ · nH ₂ O, Zr (O ₃ P—R ¹ —SO ₃ H) ₂ , Zr (O ₃ P—R ¹ —SO ₃ H) ₂ .nH ₂ O, Zr (O ₃ P—R ^{2 _{-SO 3 H) 2-x (}} O 3 P-R 3 -COOH) x, and ^{_{Zr (O 3 P-R 2}} -SO 3 H) 2-x (O 3 P-R 3 -COOH) x · nH ₂ O (wherein R ¹ , R ² and R ³ each independently represents a divalent aromatic group, preferably R ¹ and R ² each independently represents a divalent aromatic group and R ³ is preferably at least one selected from the group consisting of an alkylene group.

<107> In the above <105>, the titanium compound includes TiO ₂ , TiO ₂ .nH ₂ O, Ti (HPO ₄ ) ₂ , Ti (HPO ₄ ) ₂ .nH ₂ O, Ti (HSO ₃ ) ₂ , and It may be at least one selected from the group consisting of Ti (HSO ₃ ) ₂ .nH ₂ O. In the above <105>, the cerium compound is at least one selected from the group consisting of CeO ₂ , CeO ₂ .nH ₂ O, Ce (HPO ₄ ) ₂ and Ce (HPO ₄ ) ₂ .nH ₂ O. Good. In the above <105>, the uranium compound is selected from the group consisting of H ₃ OUO ₄ PO ₄ , H ₃ OUO ₄ PO ₄ .nH ₂ O, H ₃ OUO ₂ AsO ₄ and H ₃ OUO ₂ AsO ₄ .nH ₂ O. It is good that it is at least one kind. In the above <105>, the tin compound may be SnO ₂ or SnO ₂ · nH ₂ O. In the above <105>, the vanadium compound may be V ₂ O ₅ or V ₂ O ₅ .nH ₂ O. In the above item <105>, antimony _{compounds, Sb 2 O 5, Sb 2} O 5 · nH 2 O, HSbO 3, HSbO 3 · nH 2 O, H 2 SbO 11, H 2 SbO 11 · nH 2 O, H x At least one selected from the group consisting of Sb _x P ₂ O ₃ and H _x Sb _x P ₂ O ₃ .nH ₂ O (wherein x is 1, 3 or 5 and n is 2 to 10). It is good to be. In the above <105>, calcium hydroxyapatite and hydrated calcium hydroxyapatite are Ca ₁₀ (PO ₄ ) X ₂ and Ca ₁₀ (PO ₄ ) X ₂ .nH ₂ O (wherein X is —OH and / or Or at least one selected from the group consisting of -F).

<108> In any one of the above items <98> to <107>, the proton-conductive inorganic nanoparticles have a Stokes particle size of 20 nm or less, preferably 10 nm or less, more preferably 5 nm or less by a dynamic light scattering method. Is good.
<109> In any one of the above <98> to <108>, the proton conductive inorganic nanoparticles are on the order of 1 × 10 ⁻⁵ S / cm, preferably 1 × 10 ⁻³ S at a temperature of 20 to 150 ° C. Proton conductivity in the order of / cm, more preferably in the order of 1 × 10 ⁻² S / cm.
<110> In any one of the above items <98> to <109>, the proton conductive polymer is one or more of a hydrocarbon-based polymer group that can be dissolved in a polar organic solvent, preferably heat resistant. It may be one or more of the functional hydrocarbon-based polymer group.

<111> In any one of the above items <99> to <110>, the polar organic solvent may be selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide and 1-methylpyrrolidone.
<112> In any one of the above items <98> to <111>, the proton conductive polymer may be one or more of a sulfonated hydrocarbon polymer group.

<113> A dispersion having proton conductive inorganic nanoparticles or the proton conductive inorganic nanoparticle precursor and a polar organic solvent, wherein the proton conductive inorganic nanoparticles or the precursor thereof are uniform in the polar organic solvent. And the proton-conductive inorganic nanoparticles or precursors thereof having a Stokes particle size of 20 nm or less, preferably 10 nm or less, more preferably 5 nm or less, and most preferably 2 nm or less, as determined by dynamic light scattering, Dispersion.
<114> In the above <113>, the polar organic solvent may be selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide.

<115> In the above <113> or <114>, the proton conductive inorganic nanoparticles or precursors thereof are zirconium compound, titanium compound, cerium compound, uranium compound, tin compound, vanadium compound, antimony compound, and calcium hydroxy It may be at least one selected from the group consisting of apatite and hydrated calcium / hydroxyapatite, and is preferably a zirconium compound.
<116> In the above <115>, the zirconium compound contains ZrO ₂ , ZrO ₂ .nH ₂ O, Zr (HPO ₄ ) ₂ , Zr (HPO ₄ ) ₂ .nH ₂ O, Zr (HSO ₃ ) ₂ , Zr (HSO ₃ ) ₂ · nH ₂ O, Zr (O ₃ P—R ¹ —SO ₃ H) ₂ , Zr (O ₃ P—R ¹ —SO ₃ H) ₂ .nH ₂ O, Zr (O ₃ P—R ^{2 _{-SO 3 H) 2-x (}} O 3 P-R 3 -COOH) x, and ^{_{Zr (O 3 P-R 2}} -SO 3 H) 2-x (O 3 P-R 3 -COOH) x · nH ₂ O (wherein R ¹ , R ² and R ³ each independently represents a divalent aromatic group, preferably R ¹ and R ² each independently represents a divalent aromatic group and R ³ is preferably at least one selected from the group consisting of an alkylene group.

<117> In the above <115>, the titanium compound includes TiO ₂ , TiO ₂ .nH ₂ O, Ti (HPO ₄ ) ₂ , Ti (HPO ₄ ) ₂ .nH ₂ O, Ti (HSO ₃ ) ₂ , and It may be at least one selected from the group consisting of Ti (HSO ₃ ) ₂ .nH ₂ O. In the above <115>, the cerium compound is at least one selected from the group consisting of CeO ₂ , CeO ₂ .nH ₂ O, Ce (HPO ₄ ) ₂ and Ce (HPO ₄ ) ₂ .nH ₂ O. Good. In the above <115>, the uranium compound is selected from the group consisting of H ₃ OUO ₄ PO ₄ , H ₃ OUO ₄ PO ₄ .nH ₂ O, H ₃ OUO ₂ AsO ₄ and H ₃ OUO ₂ AsO ₄ .nH ₂ O. It is good that it is at least one kind. In the above <115>, the tin compound may be SnO ₂ or SnO ₂ .nH ₂ O. In the above <115>, the vanadium compound may be V ₂ O ₅ or V ₂ O ₅ .nH ₂ O. In the above item <115>, antimony _{compounds, Sb 2 O 5, Sb 2} O 5 · nH 2 O, HSbO 3, HSbO 3 · nH 2 O, H 2 SbO 11, H 2 SbO 11 · nH 2 O, H x At least one selected from the group consisting of Sb _x P ₂ O ₃ and H _x Sb _x P ₂ O ₃ .nH ₂ O (wherein x is 1, 3 or 5 and n is 2 to 10). It is good to be. In the above <115>, calcium hydroxyapatite and hydrated calcium hydroxyapatite are Ca ₁₀ (PO ₄ ) X ₂ and Ca ₁₀ (PO ₄ ) X ₂ .nH ₂ O (wherein X is —OH and / or Or at least one selected from the group consisting of -F).
<118> In any one of the above <113> to <117>, the proton conductive inorganic nanoparticles are on the order of 1 × 10 ⁻⁵ S / cm, preferably 1 × 10 ⁻³ S at a temperature of 20 to 150 ° C. Proton conductivity in the order of / cm, more preferably in the order of 1 × 10 ⁻² S / cm.

<119> A method for producing a dispersion having proton conductive inorganic nanoparticles or a proton conductive inorganic nanoparticle precursor and a polar organic solvent, the method comprising:
i) preparing proton conductive inorganic nanoparticles or precursors thereof; and
ii) having the step of uniformly dispersing the proton conductive nano-inorganic particles or precursors thereof in the polar organic solvent,
The above method, wherein the proton-conductive inorganic nanoparticles or precursors thereof have a Stokes particle size of 20 nm or less, preferably 10 nm or less, more preferably 5 nm or less, and most preferably 2 nm or less by a dynamic light scattering method.

<120> In the above <119>, the step of preparing the proton-conductive nano-inorganic particles or a precursor thereof,
Preparing a solution of an organic solvent of a metal alkoxide (where the metal is selected from the group consisting of zirconium, titanium, cerium, uranium, tin, vanadium, arsenic and calcium); and hydrolyzing the solution to provide the proton conductivity A step of obtaining nano-inorganic particles or a precursor thereof.
<121> In the above <119> or <120>, the polar organic solvent may be selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide.

<122> In any one of the above <119> to <121>, the proton conductive inorganic nanoparticles or a precursor thereof may be a zirconium compound, a titanium compound, a cerium compound, a uranium compound, a tin compound, a vanadium compound, an antimony compound, and It may be at least one selected from the group consisting of calcium hydroxyapatite and hydrated calcium hydroxyapatite, preferably a zirconium compound.
<123> In the above <122>, the zirconium compound contains ZrO ₂ , ZrO ₂ .nH ₂ O, Zr (HPO ₄ ) ₂ , Zr (HPO ₄ ) ₂ .nH ₂ O, Zr (HSO ₃ ) ₂ , Zr (HSO ₃ ) ₂ · nH ₂ O, Zr (O ₃ P—R ¹ —SO ₃ H) ₂ , Zr (O ₃ P—R ¹ —SO ₃ H) ₂ .nH ₂ O, Zr (O ₃ P—R ^{2 _{-SO 3 H) 2-x (}} O 3 P-R 3 -COOH) x, and ^{_{Zr (O 3 P-R 2}} -SO 3 H) 2-x (O 3 P-R 3 -COOH) x · nH ₂ O (wherein R ¹ , R ² and R ³ each independently represents a divalent aromatic group, preferably R ¹ and R ² each independently represents a divalent aromatic group and R ³ is preferably at least one selected from the group consisting of an alkylene group.

<124> In the above <122>, the titanium compound includes TiO ₂ , TiO ₂ · nH ₂ O, Ti (HPO ₄ ) ₂ , Ti (HPO ₄ ) ₂ · nH ₂ O, Ti (HSO ₃ ) ₂ , and It may be at least one selected from the group consisting of Ti (HSO ₃ ) ₂ .nH ₂ O. In the above <115>, the cerium compound is at least one selected from the group consisting of CeO ₂ , CeO ₂ .nH ₂ O, Ce (HPO ₄ ) ₂ and Ce (HPO ₄ ) ₂ .nH ₂ O. Good. In the above item <122>, uranium _compounds, selected from _{H 3 OUO 4 PO 4, H} 3 OUO 4 PO 4 · nH 2 O, H 3 OUO 2 AsO 4 and _{H 3 OUO 2 AsO 4 · nH} 2 O consisting of the group It is good that it is at least one kind. In the above <122>, the tin compound may be SnO ₂ or SnO ₂ .nH ₂ O. In the above <122>, the vanadium compound may be V ₂ O ₅ or V ₂ O ₅ .nH ₂ O. In the above item <122>, antimony _{compounds, Sb 2 O 5, Sb 2} O 5 · nH 2 O, HSbO 3, HSbO 3 · nH 2 O, H 2 SbO 11, H 2 SbO 11 · nH 2 O, H x At least one selected from the group consisting of Sb _x P ₂ O ₃ and H _x Sb _x P ₂ O ₃ .nH ₂ O (wherein x is 1, 3 or 5 and n is 2 to 10). It is good to be. In the above <122>, calcium hydroxyapatite and hydrated calcium hydroxyapatite are Ca ₁₀ (PO ₄ ) X ₂ and Ca ₁₀ (PO ₄ ) X ₂ .nH ₂ O (wherein X is —OH and / or Or at least one selected from the group consisting of -F).
<125> In any one of the above items <119> to <124>, the proton-conductive inorganic nanoparticles are in the order of 1 × 10 ⁻⁵ S / cm, preferably 1 × 10 ⁻³ S at a temperature of 20 to 150 ° C. Proton conductivity in the order of / cm, more preferably in the order of 1 × 10 ⁻² S / cm.

  <126> A proton conductive hybrid material having a proton conductive inorganic mesoporous material and a proton conductive polymer, wherein the proton conductive inorganic mesoporous material has a pore diameter of 20 nm or less, preferably 10 nm or less, more preferably 5 nm or less. Most preferably, the material is 2 nm or less. Preferably, the proton conductive polymer is disposed in the vicinity of the pores of the proton conductive inorganic mesoporous material, and more preferably, the proton conductive inorganic porous material is disposed around the proton conductive polymer. It is better.

<127> In the above <126>, the proton conductive inorganic mesoporous material includes a mesoporous zirconium compound, a mesoporous titanium compound, a mesoporous cerium compound, a mesoporous uranium compound, a mesoporous tin compound, a mesoporous vanadium compound, a mesoporous antimony compound, and a mesoporous calcium hydroxy It may be at least one selected from the group consisting of apatite and mesoporous hydrated calcium / hydroxyapatite, and is preferably a mesoporous zirconium compound. In particular, the mesoporous compound may have a functional group. Examples of the functional group include —SO ₃ H, —PO _{4 and the} like, but are not limited thereto.
<128> In the above <127>, the mesoporous zirconium compound includes mesoporous ZrO ₂ , mesoporous ZrO ₂ .nH ₂ O, mesoporous Zr (HPO ₄ ) ₂ , mesoporous Zr (HPO ₄ ) ₂ .nH ₂ O, and mesoporous Zr ( HSO ₃ ) ₂ , mesoporous Zr (HSO ₃ ) ₂ .nH ₂ O, mesoporous Zr (O ₃ P—R ¹ —SO ₃ H) ₂ , mesoporous Zr (O ₃ P—R ¹ —SO ₃ H) ₂ .nH ₂ O, mesoporous Zr (O ₃ P—R ² —SO ₃ H) _2−x (O ₃ P—R ³ —COOH) _x , and mesoporous Zr (O ₃ P—R ² —SO ₃ H) _{2−x ^{(O 3 P-R 3 -COOH}} ) x · nH 2 O ( ^wherein, R 1, ^{R 2,} and ^{R 3} each independently represent a divalent aromatic group, preferably R ¹ and R ² and R ³ each independently represent a divalent aromatic group it may be at least one selected from the group consisting of an alkylene group). In particular, the mesoporous zirconium compound preferably has a functional group. Examples of the functional group include —SO ₃ H, —PO _{4 and the} like, but are not limited thereto.

<129> In the above <127>, the mesoporous titanium compound includes mesoporous TiO ₂ , mesoporous TiO ₂ · nH ₂ O, mesoporous Ti (HPO ₄ ) ₂ , mesoporous Ti (HPO ₄ ) ₂ · nH ₂ O, mesoporous Ti ( It may be at least one selected from the group consisting of HSO ₃ ) ₂ and mesoporous Ti (HSO ₃ ) ₂ .nH ₂ O. In the above <127>, the mesoporous cerium compound is at least 1 selected from the group consisting of mesoporous CeO ₂ , mesoporous CeO ₂ · nH ₂ O, mesoporous Ce (HPO ₄ ) ₂ and mesoporous Ce (HPO ₄ ) ₂ · nH ₂ O. It should be a seed. In the above <127>, the mesoporous uranium compounds are mesoporous H ₃ OUO ₄ PO ₄ , mesoporous H ₃ OUO ₄ PO ₄ .nH ₂ O, mesoporous H ₃ OUO ₂ AsO ₄ and mesoporous H ₃ OUO ₂ AsO ₄ .nH ₂ O. It is good that it is at least one selected from the group consisting of In the above <127>, the mesoporous tin compound may be mesoporous SnO ₂ or mesoporous SnO ₂ · nH ₂ O. In the above <127>, the mesoporous vanadium compound may be mesoporous V ₂ O ₅ or mesoporous V ₂ O ₅ .nH ₂ O. In the above <127>, the mesoporous antimony compound is mesoporous Sb ₂ O ₅ , mesoporous Sb ₂ O ₅ .nH ₂ O, mesoporous HSbO ₃ , mesoporous HSbO ₃ .nH ₂ O, mesoporous H ₂ SbO ₁₁ , and mesoporous H ₂ SbO _11. NH ₂ O, mesoporous H _x Sb _x P ₂ O ₃ and mesoporous H _x Sb _x P ₂ O ₃ .nH ₂ O (wherein x is 1, 3 or 5 and n is 2 to 10) It is good that it is at least one selected from the group consisting of In the above <127>, mesoporous calcium hydroxyapatite and mesoporous hydrated calcium hydroxyapatite are mesoporous Ca ₁₀ (PO ₄ ) X ₂ and mesoporous Ca ₁₀ (PO ₄ ) X ₂ .nH ₂ O (wherein X is It may be at least one selected from the group consisting of -OH and / or -F). In particular, each mesoporous compound should have a functional group. Examples of the functional group include —SO ₃ H, —PO _{4 and the} like, but are not limited thereto.

<130> In any one of the above <126> to <129>, the proton conductive inorganic mesoporous material is on the order of 1 × 10 ⁻⁵ S / cm, preferably 1 × 10 ⁻³ S at a temperature of 20 to 150 ° C. Proton conductivity in the order of / cm, more preferably in the order of 1 × 10 ⁻² S / cm.
<131> In any one of the above items <126> to <130>, the proton conductive polymer is one or more of a hydrocarbon-based polymer group, preferably heat-resistant, which can be dissolved in a polar organic solvent. It may be one or more of the functional hydrocarbon polymer group.
<132> In the above <131>, the polar organic solvent is a group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide, preferably N, N-dimethylformamide, dimethyl sulfoxide and 1 -Preferably selected from the group consisting of methylpyrrolidone.

<133> In any one of the above items <126> to <132>, the proton conductive polymer may be one or more of a sulfonated hydrocarbon polymer group.
<134> In any one of the above items <126> to <133>, the proton conductive polymer may be chemically bonded to the proton conductive inorganic mesoporous material.
<135> In any one of the above <126> to <134>, the proton conductive hybrid material has a proton conductivity of 10 ⁻³ S / cm to low temperature and high humidity at a temperature of −20 to 150 ° C. It should be 1 S / cm.

<136> A fuel cell comprising the proton conductive hybrid material according to any one of the above <1> to <11>.
<137> A fuel cell having the catalyst layer of any one of the above <46> to <62>.
<138> A fuel cell having the electrolyte membrane according to any one of <85> to <97>.

<139> A fuel cell comprising the proton-conductive hybrid material according to any one of the above <126> to <135>.
<140> A catalyst layer for a fuel cell, comprising the proton conductive hybrid material according to any one of the above <126> to <135>.
<141> A fuel cell having the catalyst layer of <140> above.
<142> An electrolyte membrane for a fuel cell, comprising the proton conductive hybrid material according to any one of the above <126> to <135>.
<143> A fuel cell having the electrolyte membrane of <142> above.

The present invention can provide an organic-inorganic hybrid material capable of providing high proton conductivity in a wide range from low temperature to high temperature.
In addition to the above effects, the present invention can provide an organic-inorganic hybrid material that can provide high proton conductivity in a wide temperature range and low humidity.
Further, according to the present invention, in addition to the above effect or in addition to the above effect, the particle size is small, that is, a particle size that can reach the pores of primary particles such as carbon powder. Proton conducting materials can be provided.
Further, according to the present invention, it is possible to provide a fuel cell catalyst layer and a fuel cell electrolyte membrane using the above materials, and a fuel cell using these.
Furthermore, according to the present invention, it is possible to provide a method for producing the above materials, catalyst layers, electrolyte membranes, and fuel cells.

Hereinafter, the present invention will be described in detail.
<Proton conductive hybrid material>
The present invention provides a proton conductive hybrid material having proton conductive inorganic nanoparticles and a proton conductive polymer. In particular, the proton conductive hybrid material of the present invention is characterized in that the Stokes particle size by dynamic light scattering method is 20 nm or less, preferably 10 nm or less, more preferably 5 nm or less.
In addition, the proton-conductive hybrid material may be 10 ⁻³ S / cm to 1 S / cm at a temperature of −20 to 150 ° C. under low and high humidity.
Furthermore, in the material of the present invention, the proton conducting polymer may be chemically bonded to the proton conducting inorganic nanoparticles.

  The material of the present invention is an organic-inorganic hybrid material and can provide high proton conductivity in a wide range from low temperature to high temperature. In addition, the material of the present invention can provide high proton conductivity in a wide temperature range and low humidity. In addition, the material of the present invention has a sufficiently small Stokes particle size, for example, a particle size that can reach the pores of primary particles such as carbon powder. Can be used.

  In the material of the present invention, the proton conductive polymer is preferably disposed in the vicinity of the proton conductive inorganic nanoparticles, and more preferably, the proton conductive polymer is disposed around the proton conductive inorganic nanoparticles. Good.

  Proton conductive inorganic nanoparticles in the material of the present invention include zirconium compounds, titanium compounds, cerium compounds, uranium compounds, tin compounds, vanadium compounds, antimony compounds, and calcium hydroxyapatite and hydrated calcium hydroxyapatite. It should be at least one selected, and is preferably a zirconium compound.

Among the above, zirconium compounds include ZrO ₂ , ZrO ₂ .nH ₂ O, Zr (HPO ₄ ) ₂ , Zr (HPO ₄ ) ₂ .nH ₂ O, Zr (HSO ₃ ) ₂ , Zr (HSO ₃ ) _2. nH ₂ O, Zr (O ₃ P—R ¹ —SO ₃ H) ₂ , Zr (O ₃ P—R ¹ —SO ₃ H) ₂ .nH ₂ O, Zr (O ₃ P—R ² —SO ₃ H) ) _2-x (O ₃ P—R ³ —COOH) _x , and Zr (O ₃ P—R ² —SO ₃ H) _2-x (O ₃ P—R ³ —COOH) _x · nH ₂ O (formula R ¹ , R ² , and R ³ each independently represent a divalent aromatic group, preferably R ¹ and R ² each independently represent a divalent aromatic group, and R ³ represents an alkylene group. At least one selected from the group consisting of:

Titanium compounds include TiO ₂ , TiO ₂ · nH ₂ O, Ti (HPO ₄ ) ₂ , Ti (HPO ₄ ) ₂ · nH ₂ O, Ti (HSO ₃ ) ₂ , and Ti (HSO ₃ ) ₂ · nH. _It is good that it is at least one selected from the group consisting of ₂ O.
The cerium compound may be at least one selected from the group consisting of CeO ₂ , CeO ₂ .nH ₂ O, Ce (HPO ₄ ) ₂ and Ce (HPO ₄ ) ₂ .nH ₂ O.
Uranium compounds _{are H 3 OUO 4 PO 4, H} 3 OUO 4 PO 4 · nH 2 O, H 3 OUO 2 AsO 4 and _H 3 _OUO 2 _AsO least one selected from the group consisting of 4 · nH ₂ O It is good.

The tin compound may be SnO ₂ or SnO ₂ .nH ₂ O.
The vanadium compound may be V ₂ O ₅ or V ₂ O ₅ .nH ₂ O.
Antimony _{compounds, Sb 2 O 5, Sb 2} O 5 · nH 2 O, HSbO 3, HSbO 3 · nH 2 O, H 2 SbO 11, H 2 SbO 11 · nH 2 O, H x Sb x P 2 O 3 And at least one selected from the group consisting of H _x Sb _x P ₂ O ₃ .nH ₂ O (wherein x is 1, 3 or 5 and n is 2 to 10).
Calcium hydroxyapatite and hydrated calcium hydroxyapatite are Ca ₁₀ (PO ₄ ) X ₂ and Ca ₁₀ (PO ₄ ) X ₂ .nH ₂ O (wherein X represents —OH and / or —F). It is good that it is at least one selected from the group consisting of

The proton conductive inorganic nanoparticles of the present invention may have a Stokes particle size of 20 nm or less, preferably 10 nm or less, more preferably 5 nm or less by dynamic light scattering.
The proton conductive inorganic nanoparticles are in the order of 1 × 10 ⁻⁵ S / cm, preferably in the order of 1 × 10 ⁻³ S / cm, more preferably 1 × 10 ⁻² S at a temperature of 20 to 150 ° C. It is preferable to have proton conductivity on the order of / cm.

Furthermore, the proton-conductive inorganic nanoparticles of the present invention have the following 1. And 2. It can also be formed as follows.
1. Structure and surface modification of layered zirconium phosphate Synthesis of zirconium phosphate In zirconia phosphorylated, surface transport is dominant in conductivity. That is, steric effects, steric effects of proton species on the surface, diffusion, and rearrangement are easier than in bulk. In addition, since the ionic group on the surface is more easily hydrated than the inner one, protonation of water is promoted.
The distance between adjacent phosphate groups (0.53 nm) (see FIG. 5) is so large that proton diffusion cannot occur without the presence of water molecules bridging between P—OH groups. Ultimately, the number and arrangement of these molecules determine the conduction properties.
When the pendant group R of α-Zr (RPO ₃ ) ₂ contains a polar group having an exchangeable proton such as —COOH, —SO ₃ H, the compound is also known as phosphoric acid, and has an inorganic main chain. It has an organic ion exchange group. These materials are interesting because of the long chain thermal vibrations. The terminal acid groups can approach each other at a distance shorter than the distance between adjacent PO3 sites (0.53 nm). Thus, protons jump one after another along the acid group along the mechanism (Tarzan Mechanism).
Thus, zirconium phosphate having —SO ₃ H bonded to a long aliphatic chain, and mixed phosphate group zirconium phosphate having —SO ₃ H and —COOH bonded to a long aliphatic chain were synthesized. It is better. Such materials will increase proton conductivity by a factor of 2-3 compared to normal ZrP.

2. Synthesis and function of mesoporous / nanoporous zirconium hydrogen phosphate Nano-sized hexagonal mesoporous zirconia is preferably synthesized by a self-assembly technique. The inner wall should be functionalized with aromatic sulfonic acid groups. A homogeneous nanocomposite should be prepared and applied to the pore filling membrane.
Also, the proton conducting material to be developed should be a derivative of hydrated zirconia, sulfonated zirconia and phosphorylated zirconia doped with other oxides such as titania and alumina.

Of the materials of the present invention, the proton conducting polymer is one or more of a group of hydrocarbon polymers, preferably one of a group of heat resistant hydrocarbon polymers, that can be dissolved in a polar organic solvent. It may be one or more.
Here, the polar organic solvent is a group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide, preferably a group consisting of N, N-dimethylformamide, dimethyl sulfoxide and 1-methylpyrrolidone. It is good to be chosen from.

  As hydrocarbon polymers, polyether ketone, polysulfide, polyphosphazene, polyphenylene, polybenzimidazole, polyethersulfone, polyphenylene oxide, polycarbonate, polyurethane, polyamide, polyimide, polyurea, polysulfone, polysulfonate, polybenzoxazole, polybenzo Thiazole, polythiazole, polyphenylquinoxaline, polyquinoline, polysiloxane, polytriazine, polydiene, polypyridine, polypyrimidine, polyoxathiazole, polytetrazabilene, polyoxazole, polyvinylpyridine, polyvinylimidazole, polypyrrolidone, polyacrylate derivative, poly A methacrylate derivative, a polystyrene derivative, etc. can be mentioned. Preferably, polyether ketone, polysulfide, polyphosphazene, polyphenylene, polybenzimidazole, polyethersulfone, polyphenylene oxide, polycarbonate, polyurethane, polyamide, polyimide, polyurea, polysulfone, polysulfonate, polybenzoxazole, polybenzothiazole, poly Examples thereof include phenylquinoxaline, polyquinoline, polytriazine, polydiene, polypyridine, polyoxathiazole, polyacrylate derivative, polymethacrylate derivative, and polystyrene derivative. More preferably, polyetherketone, polysulfide, polyphosphazene, polyphenylene, polybenzimidazole, polyethersulfone, polyphenylene oxide, polycarbonate, polyamide, polyimide, polyurea, polysulfone, polysulfonate, polybenzoxazole, polybenzothiazole, polyphenyl Examples thereof include quinoxaline, polyquinoline, polytriazine, polydiene, polyacrylate derivative, polymethacrylate derivative, and polystyrene derivative.

The proton conducting polymer may have a proton acid group. Examples of proton acid groups include sulfonic acid groups, carboxylic acid groups, phosphonic acid groups, alkyl sulfonic acid groups, alkyl carboxylic acid groups, alkyl phosphonic acid groups, phosphoric acid groups, and phenolic hydroxyl groups. It is not limited.
The proton conductive polymer has an ion exchange capacity of 0.1 to 4.5 meq / g, preferably 0.2 to 4.0 meq / g, more preferably 0.25 to 4.5 meq / g. . Here, the ion exchange capacity indicates the number of milliequivalents per 1 g of polymer (meq / g).

  The proton conducting polymer may be one or more of a group of sulfonated hydrocarbon-based polymers.

  The proton conductive polymer may be sulfonic acid group-containing polyethersulfone, sulfonic acid group-containing polyetherketone, sulfonic acid group-containing polyetheretherketone, sulfonic acid group-containing polyimide, or the like.

  Examples of the proton conductive polymer include the following sulfonated polymers. SPEK: sulfonated polyetheretherketone, SPEK: sulfonated polyetherketone, SPES: polyethersulfone, SP3O: poly (2,6-diphenyl-4-phenylene oxide), SPPBP: sulfonated poly (4-phenoxy) Benzoyl-1,4-phenylene), SPPO: sulfonated polyphenylene oxide or poly (2,6-dimethyl-1,4-phenylene oxide), SPPQ: poly (phenylquinosaline), SPS: sulfonated polystyrene, SPSF: Sulfonated polysulfone, SPSU: sulfonated polysulfone Udel.

<Dispersion with proton conductive hybrid material and polar organic solvent>
The present invention provides a dispersion comprising the proton conductive hybrid material and a polar organic solvent.
In the dispersion of the present invention, the proton conductive hybrid material is uniformly dispersed in a polar organic solvent selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide. As described above, the proton conductive hybrid material has proton conductive inorganic nanoparticles and a proton conductive polymer.
In the dispersion of the present invention, the Stokes particle size of the proton conductive hybrid material by dynamic light scattering method is 20 nm or less, preferably 10 nm or less, more preferably 5 nm or less. In addition, the proton conductive polymer is preferably disposed in the vicinity of the proton conductive inorganic nanoparticles, and more preferably, the proton conductive polymer is disposed around the proton conductive inorganic nanoparticles. The proton conductive polymer may be chemically bonded to the proton conductive inorganic nanoparticles.
In addition, about the characteristic of a proton conductive inorganic nanoparticle and a proton conductive polymer, it is the same as that of the above-mentioned.
The polar organic solvent may be selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide and 1-methylpyrrolidone.

<Production method of dispersion>
The dispersion described above can be prepared, for example, by the following method.
That is, the preparation method is
Dissolving a proton conductive polymer in a first polar organic solvent selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide to obtain a polymer solution;
Proton conductive inorganic in a second polar organic solvent selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide which is the same as or different from the first polar organic solvent Dispersing the nanoparticles to obtain a nanoparticle dispersion; and pouring the polymer solution into the nanoparticle dispersion or pouring the nanoparticle dispersion into the polymer solution, the dispersion having a polar organic solvent and a proton conducting hybrid material Obtaining a body;
Have

  You may further have the process of adding the poor organic solvent with respect to a proton conductive polymer to the obtained dispersion, and obtaining the dispersion which has a proton-conductive hybrid material with a still smaller Stokes particle size. Here, the poor organic solvent may be selected from the group consisting of methanol, ethanol, isopropanol, butanol and hexane, and is preferably isopropanol.

  The first and / or second polar organic solvent may be selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide and 1-methylpyrrolidone.

  In the process of pouring the polymer solution into the nanoparticle dispersion or the process of pouring the nanoparticle dispersion into the polymer solution, the proton conducting polymer reacts with the proton conducting inorganic nanoparticles, and a part or all of one end of the proton conducting polymer is You may make it chemically couple | bond with a proton conductive inorganic nanoparticle.

<Production method of hybrid material>
The proton conductive hybrid material described above can be prepared by the following method.
That is, this method
Dissolving a proton conductive polymer in a first polar organic solvent selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide to obtain a polymer solution;
Proton conductive inorganic in a second polar organic solvent selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide which is the same as or different from the first polar organic solvent Dispersing the nanoparticles to obtain a nanoparticle dispersion; and pouring the polymer solution into the nanoparticle dispersion or pouring the nanoparticle dispersion into the polymer solution to disperse with a polar organic solvent and a proton conducting hybrid material Obtaining a body; and removing the first and second polar organic solvents from the obtained dispersion to obtain a proton conductive hybrid material.
The first and / or second polar organic solvent may be selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide and 1-methylpyrrolidone.

After the dispersion is obtained, the dispersion may further include a step of adding a poor organic solvent for the proton conductive polymer to obtain a dispersion having a proton conductive hybrid material having a smaller Stokes particle size. . Here, as a poor organic solvent, the same thing as the manufacturing method of a dispersion can be used.
Also, in the step of pouring the polymer solution into the nanoparticle dispersion or the step of pouring the nanoparticle dispersion into the polymer solution, the proton conductive polymer reacts with the proton conductive inorganic nanoparticles, and a part of the proton conductive polymer Alternatively, all one ends may be chemically bonded to the proton-conductive inorganic nanoparticles.
As described above, the proton conductive hybrid material can use the above-described dispersion preparation method.

<Catalyst layer>
The present invention provides a catalyst layer for a fuel cell having the proton conductive hybrid material described above. In particular, the present invention provides a fuel cell catalyst layer comprising an electron conductor, a catalyst, and a proton conductive hybrid material.
The catalyst layer has an electron conductor, a catalyst, and a proton conductive hybrid material. As the proton conductive hybrid material, materials having various characteristics described above can be used.

The catalyst layer is preferably configured such that the catalyst is supported on the surface of the electron conductor and the proton conductive hybrid material is disposed in the vicinity of the position where the catalyst is disposed.
The proton conducting hybrid material may be physically and / or chemically bonded to the electronic conductor.

The electron conductor may be a carbon-based porous electron conductor or a metal-based porous electron conductor, and is preferably a carbon-based porous electron conductor.
The carbon-based porous electronic conductor may be selected from the group consisting of carbon black, acetylene black, graphite, carbon fiber, carbon nanotube, fullerene, activated carbon, and glass carbon.
The particle diameter of the electron conductor is 300 nm or less, preferably 100 nm or less, more preferably 30 nm or less.

The catalyst may be selected from the group consisting of a noble metal catalyst group and an organic catalyst group. Examples of the noble metal catalyst include, but are not limited to, Pt and Pt—Ru.
The catalyst may have a particle size of 30 nm or less, preferably 10 nm or less, more preferably 3 nm or less.

<Production method of catalyst layer>
The above fuel cell catalyst layer can be prepared by the following method.
That is, this method
a) supporting a catalyst on an electronic conductor;
b) preparing a proton conductive hybrid material dispersion in which the proton conductive hybrid material is dispersed in a polar organic solvent;
c) mixing the dispersion with an electron conductor carrying a catalyst to obtain a mixture; and d) applying the mixture to a fuel cell diffusion layer to obtain a fuel cell catalyst layer;
Have
In addition, the same thing as the above-mentioned can be used for a catalyst, an electronic conductor, a proton conductive hybrid material, and a polar organic solvent.
Step b) can also use the method of preparing the dispersion described above.

It may further comprise a step of mixing the binder with the mixture during step c) or after step c) and before step d). Moreover, it is good to further have the process of removing the solvent in a mixture and adjusting the viscosity of this mixture.
In step b), the proton conducting polymer reacts with the proton conducting inorganic nanoparticles, and one or all of the ends of the proton conducting polymer are chemically bonded to the proton conducting inorganic nanoparticles. Good.

<Electrolyte membrane>
The present invention provides an electrolyte membrane having the proton conductive hybrid material described above. The electrolyte membrane for a fuel cell is preferably 10 ⁻² S / cm to 5 S / cm at a temperature of −20 to 150 ° C. under low and high humidity. A proton conductive hybrid material having the above-described characteristics can be used.
The electrolyte membrane has a substrate, and the proton conductive hybrid material may be chemically and / or physically bonded to the substrate. The substrate may be selected from the group consisting of a porous polymer and a porous ceramic. Examples of the porous polymer include polyimide and polyethylene. Examples of the porous ceramic include alumina, silica, zirconia, and titania.

  The proton conductive hybrid material may be chemically and / or physically bonded to the surface of the porous polymer or porous ceramic (including the surface of the pores).

A proton conductive hybrid material is preferably filled, fixed, and held in the pores of a substrate, particularly a porous substrate, to form an electrolyte membrane.
As the substrate, the film thickness is 0.01 to 300 μm, preferably 0.1 to 100 μm, the porosity is 10 to 95%, more preferably 40 to 90%, and the breaking strength is 1.961 × 104 kPa (200 kg / cm ² ) As described above, those having an average through-hole diameter of 0.001 to 100 μm are preferable.

When the porous substrate is a fluororesin, a known fluororesin having many carbon-fluorine bonds in the molecule can be used. Usually, a structure in which all or most of hydrogen atoms of polyolefin, preferably 50 mol% or more of hydrogen atoms are substituted with fluorine atoms can be used. In particular, it is preferable to use a structure in which all of them are substituted with fluorine atoms. By using a fluororesin as a base material, an electrolyte membrane having excellent mechanical strength, chemical stability, and heat resistance can be provided.
Fluorocarbon resins such as polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (CTFE), polyvinylidene fluoride (PVdF), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl A vinyl ether copolymer (PFA), a tetrafluoroethylene-ethylene copolymer (ETFE), a chlorotrifluoroethylene-ethylene copolymer (ECTFE), etc. can be mentioned. Polytetrafluoroethylene (PTFE) and tetrafluoroethylene-hexafluoropropylene copolymer (FEP) are preferable, and PTFE is more preferable.

Further, when a hydrocarbon resin is used as the substrate, the resin includes polyethylene, polypropylene, polycarbonate, polyimide, polyester, polyethersulfone, polyetherketone, polyetheretherketone, polysulfone, polysulfide, polyamide, polyamideimide, Polyphenylene, polyether, polyetherimide, polyetheramide and the like can be mentioned. From the viewpoint of thermal stability, they are polycarbonate, polyimide, polyester, polyethersulfone, polyetherketone, polyetheretherketone, polysulfone, polysulfide, polyamide, polyamideimide, polyphenylene, polyether, polyetherimide, and polyetheramide. Although it is preferable, it is not limited to these.
Note that a plurality of types of materials may be used for the porous substrate. For example, you may use 2 or more types from the above-mentioned fluororesin and hydrocarbon resin.

<Method for manufacturing electrolyte membrane>
The above-mentioned electrolyte membrane for fuel cells can be prepared by the following production method.
That is, the method is
x) providing a proton conductive hybrid material dispersion in which the above proton conductive hybrid material is dispersed in a polar organic solvent; and y) applying the dispersion to the pores of the substrate or to the pores and surface of the substrate; Obtaining an electrolyte membrane for a fuel cell.
In the step x), the above-described method for producing a dispersion can be used. Moreover, the above-mentioned thing can be used for a proton conductive hybrid material, a polar organic solvent, and a base material.

<Dispersion consisting of particles and solvent>
The present invention provides a dispersion comprising proton conductive inorganic nanoparticles or the proton conductive inorganic nanoparticle precursor and the above-mentioned polar organic solvent. Proton conductive inorganic nanoparticles or precursors thereof are uniformly dispersed in the polar organic solvent described above, and the proton conductive inorganic nanoparticles or precursors thereof have a Stokes particle size of 20 nm or less by a dynamic light scattering method, Preferably it has 10 nm or less, more preferably 5 nm or less, and most preferably 2 nm or less.
The proton conductive inorganic nanoparticles or the proton conductive inorganic nanoparticle precursor is the above-described proton conductive nanoparticle or a precursor thereof.

<Production method of dispersion (particles and solvent)>
The dispersion having the above-described proton conductive inorganic nanoparticles or the proton conductive inorganic nanoparticle precursor and the above polar organic solvent can be prepared by the following method.
That is, the method is
i) preparing proton conductive inorganic nanoparticles or precursors thereof; and
ii) a step of uniformly dispersing the proton conductive nano-inorganic particles or a precursor thereof in the polar organic solvent;

The step of preparing proton conductive nano inorganic particles or precursors thereof is as follows:
Preparing a solution of an organic solvent of a metal alkoxide (where the metal is selected from the group consisting of zirconium, titanium, cerium, uranium, tin, vanadium, arsenic, and calcium); and hydrolyzing the solution to proton conductive nano-inorganic A step of obtaining particles or a precursor thereof.

  The alkoxide of the metal alkoxide is a linear or branched alkyl group, preferably having 1 to 24 carbon atoms, more preferably 1 to 10 carbon atoms. For example, methyl, ethyl, propyl, butyl, i-propyl, i-butyl, pentyl, hexyl, octyl, 2-ethylhexyl, t-octyl, decyl, dodecyl, tetradecyl Group, 2-hexyldecyl group, hexadecyl group, octadecyl group, cyclohexylmethyl group, octylcyclohexyl group and the like.

The organic solvent used for the sol-gel reaction is not particularly limited as long as it dissolves the metal alkoxide. Preferably, carbonate compounds (ethylene carbonate, propylene carbonate, etc.), heterocyclic compounds (3-methyl-2-oxazolidinone, N-methylpyrrolidone, etc.), cyclic ethers (dioxane, tetrahydrofuran, etc.), chain ethers (diethyl ether) , Ethylene glycol dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene dialkyl ether, etc.), alcohols (methanol, ethanol, isopropanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, polyethylene glycol monoalkyl ether, polypropylene) Glycol monoalkyl ethers), polyhydric alcohols (ethylene glycol) , Propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, etc.), nitrile compounds (acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile, benzonitrile, etc.), esters (carboxylic esters, phosphate esters, phosphonate esters) Aprotic polar substances (dimethylsulfoxide, sulfolane, dimethylformamide, dimethylacetamide, etc.), nonpolar solvents (toluene, xylene, etc.), chlorinated solvents (methylene chloride, ethylene chloride, etc.), water, etc. can be used. .
Among these, alcohols such as ethanol and isopropanol, nitrile compounds such as acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile, and benzonitrile, and cyclic ethers such as dioxane and tetrahydrofuran are preferable. These may be used alone or in combination of two or more.

In the sol-gel reaction, a chemical modifier that can be chelated to a metal atom may be used. Examples of the chemical modifier include acetoacetate esters (such as ethyl acetoacetate), 1,3-diketones (such as acetylacetone), and acetoacetamides (such as N, N-dimethylaminoacetoacetamide). .
An acid or alkali is preferably used as a catalyst for hydrolysis and dehydration condensation polymerization of the zologel reaction. As the alkali, alkali metal hydroxide such as sodium hydroxide, ammonia and the like are common. As the acid catalyst, an inorganic or organic proton acid can be used. Examples of the inorganic protonic acid include hydrochloric acid, nitric acid, sulfuric acid, boric acid, perchloric acid, tetrafluoroboric acid, hexafluoroarsenic acid, hydrobromic acid and the like. Examples of the organic protonic acid include acetic acid, oxalic acid, and methanesulfonic acid.

  A complex oxide or the like can also be prepared by adding a solution containing the above-mentioned metal nitrate, ammonium salt, chloride salt, sulfate or the like to a metal alkoxide sol solution and then proceeding with a sol-gel reaction. Examples of the salt include, but are not limited to, aluminum nitrate, iron nitrate, zirconium oxynitrate, titanium chloride, aluminum chloride, zirconium oxychloride, titanium sulfate, and aluminum sulfate. The salt solvent is not particularly limited as long as it dissolves the salt. For example, carbonate compounds (ethylene carbonate, propylene carbonate, etc.), heterocyclic compounds (3-methyl-2-oxazolidinone, N-methylpyrrolidone, etc.) , Cyclic ethers (dioxane, tetrahydrofuran, etc.), chain ethers (diethyl ether, ethylene glycol dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene dialkyl ether, etc.), alcohols (methanol, ethanol, isopropanol, ethylene) Glycol monoalkyl ether, propylene glycol monoalkyl ether, polyethylene glycol monoalkyl ether, polypropylene glycol monoal Kill ethers), polyhydric alcohols (ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, etc.), nitrile compounds (acetonitrile, glutaronitrile, methoxyacetonitrile, propionitrile, benzonitrile, etc.), esters ( Carboxylates, phosphates, phosphonates, etc.), aprotic polar substances (dimethylsulfoxide, sulfolane, dimethylformamide, dimethylacetamide, etc.), nonpolar solvents (toluene, xylene, etc.), chlorinated solvents (methylene chloride, ethylene) Chloride, etc.), water and the like can be used.

<Hybrid material (mesoporous inorganic material)>
The present invention also provides a proton conducting hybrid material having a proton conducting inorganic mesoporous material and a proton conducting polymer. Here, the proton conductive inorganic mesoporous material has a pore diameter of 20 nm or less, preferably 10 nm or less, more preferably 5 nm or less, and most preferably 2 nm or less. Preferably, the proton conducting polymer is disposed in the vicinity of the pores of the proton conducting inorganic mesoporous material, and more preferably, the proton conducting inorganic porous material is disposed around the proton conducting polymer. .
In addition, the above-mentioned thing can be used for a proton conductive polymer.
The proton conducting polymer may be chemically bonded to the proton conducting inorganic mesoporous material.
The proton conductive hybrid material may have a proton conductivity of 10 ⁻³ S / cm to 1 S / cm at a temperature of −20 to 150 ° C. under low and high humidity.

Proton conductive inorganic mesoporous materials include mesoporous zirconium compounds, mesoporous titanium compounds, mesoporous cerium compounds, mesoporous uranium compounds, mesoporous tin compounds, mesoporous vanadium compounds, mesoporous antimony compounds, and mesoporous calcium hydroxyapatite and mesoporous hydrated calcium hydroxyapatite. It is at least one selected from the group consisting of: preferably a mesoporous zirconium compound. In particular, the mesoporous compound may have a functional group. Examples of the functional group include —SO ₃ H, —PO _{4 and the} like, but are not limited thereto.

Mesoporous zirconium compounds are mesoporous ZrO ₂ , mesoporous ZrO ₂ .nH ₂ O, mesoporous Zr (HPO ₄ ) ₂ , mesoporous Zr (HPO ₄ ) ₂ .nH ₂ O, mesoporous Zr (HSO ₃ ) ₂ , mesoporous Zr (HSO _3). ) ₂ · nH ₂ O, mesoporous Zr (O ₃ P—R ¹ —SO ₃ H) ₂ , mesoporous Zr (O ₃ P—R ¹ —SO ₃ H) ₂ .nH ₂ O, mesoporous Zr (O ₃ P—) ^{_{R 2 -SO 3 H) 2-}} x (O 3 P-R 3 -COOH) x, and mesoporous ^{_{Zr (O 3 P-R 2}} -SO 3 H) 2-x (O 3 P-R 3 -COOH) during _x · _nH 2 O ^(wherein, R 1, ^{R 2,} and ^{R 3} each independently represent a divalent aromatic group, preferably a divalent aromatic each independently ^{R 1} and ^{R 2} And at least one selected from the group consisting of R ³ represents an alkylene group. In particular, the mesoporous zirconium compound preferably has a functional group. Examples of the functional group include —SO ₃ H, —PO _{4 and the} like, but are not limited thereto.

Mesoporous titanium compounds include mesoporous TiO ₂ , mesoporous TiO ₂ · nH ₂ O, mesoporous Ti (HPO ₄ ) ₂ , mesoporous Ti (HPO ₄ ) ₂ · nH ₂ O, mesoporous Ti (HSO ₃ ) ₂ , and mesoporous Ti (HSO ₃ ) It is good that it is at least one selected from the group consisting of ₂ · nH ₂ O.
The mesoporous cerium compound may be at least one selected from the group consisting of mesoporous CeO ₂ , mesoporous CeO ₂ · nH ₂ O, mesoporous Ce (HPO ₄ ) ₂ and mesoporous Ce (HPO ₄ ) ₂ · nH ₂ O. .
The mesoporous uranium compound is selected from the group consisting of mesoporous H ₃ OUO ₄ PO ₄ , mesoporous H ₃ OUO ₄ PO ₄ .nH ₂ O, mesoporous H ₃ OUO ₂ AsO ₄ and mesoporous H ₃ OUO ₂ AsO ₄ .nH ₂ O. It is good that there is at least one kind.
The mesoporous tin compound may be mesoporous SnO ₂ or mesoporous SnO ₂ · nH ₂ O.

The mesoporous vanadium compound may be mesoporous V ₂ O ₅ or mesoporous V ₂ O ₅ .nH ₂ O.
Mesoporous antimony compounds include mesoporous Sb ₂ O ₅ , mesoporous Sb ₂ O ₅ .nH ₂ O, mesoporous HSbO ₃ , mesoporous HSbO ₃ .nH ₂ O, mesoporous H ₂ SbO ₁₁ , mesoporous H ₂ SbO _{11 so} n porous ₂ . Selected from the group consisting of H _x Sb _x P ₂ O ₃ and mesoporous H _x Sb _x P ₂ O ₃ .nH ₂ O (wherein x is 1, 3 or 5 and n is 2 to 10). It is good that there is at least one kind.
Mesoporous calcium hydroxyapatite and mesoporous hydrated calcium hydroxyapatite are mesoporous Ca ₁₀ (PO ₄ ) X ₂ and mesoporous Ca ₁₀ (PO ₄ ) X ₂ .nH ₂ O (wherein X is —OH and / or — And at least one selected from the group consisting of F).
In particular, each of the aforementioned mesoporous compounds preferably has a functional group. Examples of the functional group include —SO ₃ H, —PO _{4 and the} like, but are not limited thereto.

The proton conductive inorganic mesoporous material has an order of 1 × 10 ⁻⁵ S / cm, preferably 1 × 10 ⁻³ S / cm, more preferably 1 × 10 ⁻² S / cm at a temperature of 20 to 150 ° C. It is preferable to have proton conductivity on the order of.

<Fuel cells including the above materials>
The proton-conductive hybrid material of the present invention can be used for fuel cells, particularly fuel cell catalyst layers and fuel cell electrolyte membranes. Therefore, the present invention can provide a fuel cell having the proton conductive hybrid material of the present invention, particularly a fuel cell catalyst layer and / or a fuel cell electrolyte membrane having the proton conductive hybrid material of the present invention.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to a present Example.

  The novel concept of a pore filling membrane having superior properties compared to Nafion® is illustrated below. The pore filling membrane comprises a porous polymer substrate and a filled polymer electrolyte that fills the pores of the substrate. However, besides its excellent properties, the problem is the retention of water at high temperatures. Inorganic particles are known to retain water even at high temperatures. Therefore, the above-mentioned problem can be solved by using the polymer together with the inorganic material present uniformly in the polymer matrix. The homogenous dispersion depends on the size, properties and surface structure of the inorganic particles. Considering inorganic particles, silica is the most widely studied system. When preparing silica particles, it is easy to use silicon alkoxide. Zirconia, on the other hand, is more ideal because it is a hard material and can withstand even in harsh chemical environments. Sulfonated hydrocarbon-based polymers such as sulfonated polyethersulfone (S-PES) are attractive and suitable as proton conductors because of their low cost, commercial availability, and thermal and chemical stability If it can be wetted, it will exhibit ideal proton conductivity.

Research (at a Glance)
Concept 1. Synthesis of fully redispersed zirconia nanoparticles in polar organic solvents by controlling the hydrolysis and aggregation of zirconia alkoxides in the presence of a surface modifier. 2. Synthesis of sulfonated polyethersulfone 3. Homogeneous dispersion of inorganic nanoparticles in a nanohybrid-polymer matrix. 4. In situ synthesis of phosphorylated zirconia in polymatrix 5. Proton conductivity of hybrid electrolyte 6. Formation of a pore filling membrane by impregnating the pores of a porous polymer substrate with a nanohybrid electrolyte. Proton conductivity and fuel cell testing

A conceptual diagram of the pore filling electrolyte membrane is shown below in FIG.
Advantages of nano-hybrid pore-filled membranes High conductivity under high temperature (20-120 ° C.) and low humidity (-50% relative humidity) conditions.
2. High mechanical stability and high chemical stability.
3. Fuel crossover is controlled.
4). Polymer swelling is suppressed due to the nano-sized inorganic material and the pore walls of the membrane.

Proton conduction at high and low temperatures Nanohybrids consisting of Zr (HPO ₄ ) ₂ .nH ₂ O and SPES Under low temperature and high humidity conditions, proton conduction is a so-called vehicle mechanism (solvent water acts as a proton transfer vehicle) and a “Grotthuss” mechanism (proton transfer due to the presence of hydrogen bonds).
The different types of water associated with the polymer system are shown in FIG.
2. At high temperatures, free water associated with the system evaporates, but inorganic materials can retain water. For example, a material such as layered zirconium phosphate holds water between layers. To remove this water, a very high temperature (~ 300 ° C to 400 ° C) is required.
3. At high temperatures, proton conductivity is governed by the presence of water associated with zirconium hydrogen phosphate. This water is bonded by hydrogen bonding with P—OH of ZrP. The “Grotthuss” mechanism dominates proton conduction.
The chemical structure of zirconium hydrogen phosphate is shown in FIG.

<Synthesis of redispersed nano-zirconia precursor powder>
The most important point in the synthesis of the inorganic-organic hybrid is the dispersion characteristics of the inorganic oxide / hydroxide in a polar organic solvent. A sufficiently redispersible zirconia precursor powder is prepared by controlling the hydrolysis and aggregation of zirconium alkoxide in the presence of a surface modifier such as acetylacetone. The amount of water and the drying temperature determine the dispersion characteristics. The synthesized powder showed a high level of dispersion in polar organic solvents. Dynamic light scattering analysis was performed using a Zetasizer NanoZS (Malvern Instruments, UK) for the powder and polymer in organic solvent, 1-methylpyrrolidone (NMP) after mixing. As shown in FIG.
Nano-zirconia precursor powder that can be sufficiently redispersed in polar organic solvent was synthesized using surface modifier.

<Nanohybrid synthesis>
In situ generation of zirconium hydrogen phosphate in the SPES polymer matrix was performed by film casting after mixing the inorganic material and the polymer solution. The film was further treated with phosphoric acid to convert the homogeneously dispersed Zr ⁺ to ZrP. The film was treated with hot water to remove any excess acid present. The resulting film was transparent, indicating that the nanoparticles were highly homogeneously incorporated into the polymer matrix. Considering zirconium hydrogen phosphate, advantages include the following.
· _{SiO 2,} TiO 2 and higher conductivity than solids such as zeolites.
・ Insoluble in acid and alcohol.
-Does not elute from the membrane.
-Thermal stability and chemical stability.
-High conductivity at high temperatures even within the membrane.
In addition, Zr (HPO ₄ ) ₂ .nH ₂ O can interact with the sulfonic acid group of SPES and can dissociate protons. Zr (HPO ₄ ) ₂ .nH ₂ O can also bridge the proton exchange site of SPES, thereby shortening the proton hopping distance.
FIG. 7 shows the proton conductivity of the hybrid electrolyte at 90 ° C. under various humidity conditions. High conductivity on the order of 10 ⁻¹ has been achieved with Zr / ZrP-SPES at 90 ° C.

<1. Sol-gel synthesis of redispersed zirconia precursor powder>
A zirconia sol was prepared from zirconium alkoxide (zirconium butoxide). That is, a diluted solution (0.05M) of zirconium alkoxide was first prepared with isopropyl alcohol. During preparation of the sol, a surface modifier (acetylacetone, etc.) was dropped into the zirconium alkoxide solution with stirring, and stirring was continued for 2 hours. The ratio of metal (M) to surface modifier (L) was 1: 2. A 1M nitric acid solution was used as a hydrolysis catalyst, and in addition to the above system with vigorous stirring, a clear, transparent and stable zirconia sol was obtained. This was further stirred overnight, and the solvent was distilled off at 90 ° C. to obtain a zirconia gel. Furthermore, it dried at 90/100 degreeC for 1 day in the air dryer. This dry powder was tested for dispersion behavior in organic solvents for polymers. The dynamic light scattering feeling for Stokes particle size measurement is changed to a dynamic light scatterer (MELVERN,
Nano-2004, UK).

<2. Synthesis of proton conductive hybrid electrolyte>
A proton conducting hybrid electrolyte was synthesized by incorporating the inorganic nanoparticles described above into sulfonated polyethersulfone (S-PES).
A 20 wt% solution of S-PES was prepared by dissolving an appropriate amount of polymer in an organic polar solvent (N-methylpyrrolidone (NMP)). A required amount of powder was dissolved in an organic polar solvent (NMP) to prepare a 30 wt% solution of zirconia powder. In order to obtain hybrid electrolytes in which zirconia was incorporated into S-PES at various weight percentages, solutions with polar organic solvents containing various amounts of zirconia were blended with the S-PES solution. A self-standing hybrid film (Zr-SPES) was prepared by casting at 120 ° C. and then vacuum drying at 80 ° C. overnight without using a porous substrate.

  The resulting Zr-SPES hybrid film is diluted with a dilute solution of phosphoric acid (2M) so that the zirconia nanoparticles uniformly dispersed in the SPES polymer matrix are converted to zirconium hydrogen phosphate (ZrP-SPES). And treated at 80 ° C. for 6 hours. After the phosphoric acid treatment, the obtained ZrP-SPES film was treated with boiling water in order to remove excess phosphoric acid present in the hybrid. The proton conductivity of the hybrid film was measured using the impedance method.

  FIG. 6 is a graph showing the results of dynamic light scattering (DLS) of zirconia precursor powder redispersed in the solvents NMP and SPES / NMP. After redispersion, the Stokes diameter of the particles is 2 nm or less, as in the case of the sol as a raw material, and it can be seen from this that the precursor exhibits high dispersion characteristics. It can be seen that the diameter is in the range of 2 to 3.5 nm after mixing with the polymer solution. The slight increase in diameter may be due to the very fine aggregation of the particles in the polymer matrix. The proton conductivity values of the hybrid film under various relative humidity (RH) conditions (30% -90% RH) were measured at 90 ° C. (see FIG. 7) and 55 ° C. (see FIG. 8). And measured by the impedance method.

Compared to SPES alone, a significant increase in conductivity after modification with inorganic materials is observed. Also, an increase in conductivity is observed with the amount of inorganic material. Proton conductivity is facilitated by the dissociation of protons from hydroxy bonds and proton hopping between hydroxy groups and water molecules. As the amount of inorganic material increases, the amount of hydroxy groups increases. These can retain water even at high temperatures, resulting in higher electrical conductivity. The proton conductivity value of zirconium hydrogen phosphate incorporated in S-PES showed high conductivity compared to that compared with it. The ion source on the surface, -POH, is more hydrated than the internal one, leading to increased dissociation and increased water protonation. Proton dissociation energy is primarily measured by the hydrogen bond strength of the hydroxyl bond. A cation bonded to the hydroxyl group by a strong hydrogen bond is advantageous for increasing the conductivity. Phosphate ions are one strong candidate as strong H-bond ions. The hydrogen in P—OH bonds more strongly with water molecules. This increases the temperature required to remove water from the P-OH. Zr (HPO ₄ ) ₂ can interact with the sulfonic acid group of S-PES. It can also dissociate protons. Proton exchange can be bridged at the S-PES site. This can reduce proton hopping distances and can result in increased conductivity, as reported in the case of Nafion® modified with ZrP.

<ZrP-SPES nanohybrid-proton conduction>
Usually, the increase in conductivity is ruled out with increasing temperature. The presence of the inorganic material can increase both water uptake and water retention at high temperatures. The ratio of free water to combined water is higher in SPES than in SPES containing inorganic materials. At high temperatures, proton conduction is due to the presence of bound water present with the inorganic material. However, considering the two proton conduction mechanisms, the vehicle mechanism is dominant at low temperatures due to the presence of free water, while at high temperatures proton conduction is the gross mechanism. Mainly (Grotthhus mechanism).

Experiment <Control of hybrid particle size>
Nano-sized particles have high surface energy and can easily aggregate with neighboring particles. For inorganic solid proton conductor materials, a large surface area and interparticle distance are important. It is necessary to stabilize the particle surface. For this reason, SPES ionomer is used as a capping agent and nano-hybridized with zirconia. As shown in FIG. 10, each other attracts each other due to the adsorption force and / or the binding force. The strength of nano-hybridized zirconia and SPES is improved by (reducing agent) such as alcohol. This is because alcohol is a poor solvent for SPES. The method for controlling the particle size is as follows.

Material hydrated zirconia;
SPES ion exchange resin;
DMF (dimethylformamide); and alcohol.

Procedure 1. In a beaker containing a stir bar, 0.1375 g of a 10 wt% hydrated zirconia solution dissolved in DMF was weighed.
2. The solution was stirred with a magnetic stirrer.
3. 0.1375 g of 5 wt% DMF solution of SPES was slowly added dropwise.
4). The solution was stirred with a magnetic stirrer for 2 hours under sealing.
5. 0.15 g of the mixed solution (DMF 0.05 g and alcohol 0.1 g) was slowly added dropwise.
6). The solution was stirred with a magnetic stirrer for 30 minutes in an open system.
7). The solution was stirred with a magnetic stirrer for 6 hours in a sealed system.
Changes in the particle size distribution were detected by DLS (dynamic light scattering).

<Formation of catalyst layer>
Material Teflon (registered trademark) carbon paper (EC-TP1-060T);
Platinum-supported carbon: 46.5 wt% Pt / Ketjen black (TEC10E50E);
SPES50 ion exchange resin;
PTFE dispersion: 60 wt% dispersion in water.

Procedure 1. In a beaker containing a stir bar, 0.375 g of a hybrid ionomer having a controlled particle size was weighed.
2. 0.066 g of platinum-supported carbon was added.
3. SPES 0.0068 g was added.
4). The paste-like product was stirred with a magnetic stirrer, and the solvent was distilled off by applying ultrasonic waves until an appropriate viscosity was obtained.
5. Using a Pasteur pipette, 0.0275 g of PTFE dispersion was added and stirred for 1 minute.
6). A paste-like material was coated on the diffusion layer by screen printing.

<Structural analysis of electrode>
Mercury Pore Analysis—Primary Pore Distribution Mercury Pore Analysis is one of the most commonly used methods for qualitatively examining the pore structure of solid samples.

Bubble Point Test-Secondary Pore Distribution The result of the bubble point test indicates the secondary pore structure of the electrode.
<Determination of platinum surface area by cyclic voltammetry>
In cyclic voltammetry, the current measured is due to hydrogen adsorption and desorption on or from empty Pt sites. The charge QH (C) due to hydrogen adsorption / desorption can be obtained from a cyclic voltammogram. The total Pt surface area SPt can be estimated by the following equation.

Assuming that the atomic density of the Pt surface is 1.31 × 10 ¹⁵ (/ cm ² ), QH can be measured as a value of a cyclic voltammogram area.

<Results and discussion>
<Hybrid particle size distribution>
11 and 12 each show a size distribution by DLS. In FIG. 11, the particle size of hydrated zirconia was approximately 1.2 nm at the peak position, and the particle size of nanohybrid zirconia was changed to a broad shape by water. This indicates that the nanohybridized zirconia forms aggregates and is in an unstable state. The SPES size distribution peak shifted to the left by incorporating nanohybrid zirconia. This shows that by adding a reducing agent in FIG. 12, a smaller size is formed.

<Structural analysis of electrode>
13 and 14 show the pore size distributions by mercury pore analysis and bubble point test, respectively. In FIG. 13, the peak of the primary pore diameter of the SPES3 and hydrated zirconia hybrid electrode is located on the left side of the SPES3 electrode. This means that the hybrid ionomer can enter the primary pore more easily than the SPES3 ionomer because the size of the hybrid ionomer is smaller. In FIG. 14, the secondary pore diameter distribution of each electrode is located in almost the same region, that is, a region of 0.3 to 0.5 μm.

<Use of catalyst by cyclic voltammetry>
15 and 16 show the results of cyclic voltammetry. In FIG. 15, the utilization rate of the SPES electrode is a region surrounded by a dotted base line and a black peak line. Therefore, it can be seen that the catalyst utilization rate of the hybrid electrode is larger than that of the SPES electrode. As can be seen from FIGS. 15 and 16, it can be seen that the catalyst utilization of the modified hybrid electrode is the maximum.

<Summary>
Two effects can be obtained in hybrid ionomers incorporating nano-hydrated zirconia in SPES. One is the stabilization of the surface of the nanoparticles. The other is that the size of SPES changes from the size like the turning radius in the ratio of the molecular weight to the smaller size due to the base matrix like nanohydrated zirconia in this case. All smaller sized ionomers are associated with a pore structure such as the primary pore in the electrode. Nano-sized hybrid particles capped with high molecular weight polymers, depending on the hybrid particle size, can easily penetrate the primary pores and cover the internal surface area of the primary pores in the catalyst layer . Therefore, the utilization factor of the catalyst can be improved.

<1.1 Control of moisture content of hybrid particles>
The particle size of the hybrid electrolyte particles was controlled by reduction treatment (alcohol treatment), and the battery test was performed at a high temperature. In cyclic voltammogram (CV) measurement, it was confirmed that the hybrid particles subjected to the reduction treatment easily entered the primary pores, and the catalyst utilization rate was improved. However, changes in battery performance at high temperatures could not be confirmed by IV measurement. Therefore, the treatment shown in FIG. 17 was performed in order to improve the water holding power important for proton conduction.

<Experimental procedure>
Dissolve hydrated zirconia in a polar solvent (DMF).
Disperse SPES in zirconia solution and mix water / alcohol mixture at a certain ratio.
The mixture is allowed to stir for 1 day.
The particle size distribution of this mixed solution was confirmed by DLS measurement.
Thereafter, using these hybrid particles, a pore filling membrane and an electrode were produced. A battery test of this hybrid membrane-electrode assembly (MEA) was performed.

<1.2 Battery performance evaluation of hybrid MEA using Zirconia phosphate>
Hydrated zirconia is easily converted to Zirconia phosphate with a layer structure by phosphoric acid treatment. This ZrP is known to exhibit high proton conductivity. Therefore, using the hybrid particles prepared in Experiment 1.1, a pore filling membrane and an electrode were prepared, and then phosphoric acid treatment was performed.

Experimental Procedure Pore Filling Membrane The prepared pore filling membrane is immersed in water and fully swollen.
The membrane is soaked in 2M phosphoric acid at 80 ° C. for 6 hours.
Then, soak in pure water to wash out excess phosphoric acid.
Electrode The prepared electrode is immersed in 2M phosphoric acid at 80 ° C. for 6 hours.
Then, soak in pure water to wash out excess phosphoric acid.
Dry in a vacuum dryer.
Thereafter, hot pressing was performed to produce a hybrid MEA and a battery test was performed.

Results and Discussion 2.1 Control of moisture content of hybrid particles FIG. 18 shows the results of DLS measurement. Hybrid particles with controlled moisture content show a peak at about 3.2 nm, and hybrid particles with only reduction treatment show about 2.8 nm. Thereby, it can be seen that water could be introduced because the particle size of the particles subjected to the moisture content treatment was large.
FIG. 19 shows the results of cyclic voltammetry measurement. It can be confirmed that the catalyst utilization of the hybrid electrode is higher than that of the SPES electrode. This is thought to be due to the small size of the nano-order hybrid particles that made it easier to enter the primary pores.

FIG. 20 shows a hybrid pore filling membrane. The top of FIG. 20 is a photograph of a PI substrate (film thickness 30 μm, UPILEX-PT), and the Substrate character written on the substrate is not visible. Below, it can be seen that the hybrid particles can be filled in the pores of the base material and become transparent.
FIG. 21 shows 100 for each MEA.
Represents battery performance at ° C. It can be seen that the hybrid MEA using hybrid particles with increased moisture content has better IV characteristics than other MEAs. This is presumably because the introduced water forms hydrogen bonds with OH or SPES sulfonic acid groups on the surface of the zirconia particles, and the water retention capacity increases as a whole, and the proton conduction path can be maintained even at high temperatures.

FIG. 21 shows a pore filling membrane and electrode hybrid MEA (Membrane Electrode Assembly) using hybrid particles obtained by capping SPES based on hydrated zirconia and Zirconia phosphate pore filling membrane obtained by phosphorylation. Hybrid MEA of electrodes, and SPES of Nafion 112 membrane and SPES electrodes
IV characteristics of ME loss and IR loss free of IR loss of membrane are shown. When the temperature is higher (100 ° C) or higher, the water content necessary for proton conduction between the membrane and the electrode decreases, resulting in a decrease in power generation performance. This time, hybrid particles with improved moisture content show their effect at high temperatures, and hybrid MEA (hydrated zirconia and Zirconia phosphate) shows higher performance than Nafion 112 + SPES electrode MEA. Among hybrid MEAs, MEA using ZrP is hydrated zirconia
Higher performance than zirconia. This is thought to be due to the high proton conductivity due to the ZrP layer structure. In addition, the pore filling film is higher than the Nafion 112 film at the open electromotive force. This is considered to be because the cross-over of the fuel is less likely to occur compared to the Nafion membrane because the pore filling membrane is less likely to swell.

A conceptual diagram of a catalyst layer composed of carbon as an electron transfer path, an ionomer as a gas or proton transfer path, and a platinum catalyst as a power generation site is shown (primary pores (20 to 40 nm) and secondary pores depending on the aggregate size) (Having a complex structure of 40 nm). The conceptual diagram of a pore filling electrolyte membrane is shown. The proton conductivity mechanism of the nanohybrid composed of Zr (HPO ₄ ) ₂ · nH ₂ O and SPES is shown (proton conductivity at low temperature (effect of free water and water between layers) and proton conductivity at high temperature. (Effects of water between layers of ZrP)). It is a conceptual diagram of free water, combined water, and non-free water. It is a figure which shows the chemical structure of hydrogen hydrogen zirconium phosphate. It is a graph which shows the dynamic light scattering (DLS) analysis result of a) the zirconia precursor powder in a NMP solvent, b) the zirconia precursor powder in SPES / NMP. Graph showing conductivity at 90 ° C. of a) SPES, b) Zr (10%)-SPES, c) Zr (30%)-SPES, d) Zr (50%)-SPES and e) ZrP-SPES. It is. It is a graph which shows the electrical conductivity in 55 degreeC of SPES, Zr-SPES, and ZrP-SPES. It is a schematic diagram showing proton conductivity at low temperature (effect by free water and water between layers) and proton conductivity at high temperature (effect by water between layers of ZrP) in the ZrP-SPES system. It is a figure which shows the hybrid particle which added the inorganic nanoparticle (hybrid particle) capped with SPES, and added the reducing agent (alcohol), and controlled the particle size. It is a figure which shows the particle size distribution of the zirconia particle at the time of adding the zirconia particle in DMF and this to water. It is a figure which shows the particle size distribution in the case of Zr particle | grains in DMF, SPES3 in DMF, Zr particle | grains + SPES3 in DMF, and particle size control (reducing agent (alcohol) treatment). It is a figure which shows distribution of the primary pore of each electrode by a mercury pore analysis. It is a figure which shows distribution of the secondary pore of each electrode by a bubble point test. It is a figure which shows the cyclic voltammogram of the electrode using a hybrid, and SPES3 electrode. It is a figure which shows the cyclic voltamgram of a hybrid and modification hybrid (particle size control hybrid) reducing agent (alcohol). It is a conceptual diagram of a hybrid particle. It is a graph which shows the Stokes diameter distribution of the hybrid particle by a dynamic light scattering analysis. The measurement result of the cyclic voltammetry of a hybrid electrode and a SPES electrode is shown. It is a figure which shows the transparency of the base material before and behind the hybrid pore filling. It is a graph which shows IV performance of each MEA (hybrid MEA (ZrP), hybrid MEA (Zr), Nafion112 + SPES electrode).

Claims (143)

A proton conductive hybrid material having proton conductive inorganic nanoparticles and a proton conductive polymer, wherein the proton conductive hybrid material has a Stokes particle size of 20 nm or less by a dynamic light scattering method. material. The proton conductive inorganic nanoparticles are at least one selected from the group consisting of zirconium compounds, titanium compounds, cerium compounds, uranium compounds, tin compounds, vanadium compounds, antimony compounds, and calcium hydroxyapatite and hydrated calcium hydroxyapatite. The material of claim 1 which is a seed. The proton conductive inorganic nanoparticles are zirconium compounds, which are ZrO ₂ , ZrO ₂ .nH ₂ O, Zr (HPO ₄ ) ₂ , Zr (HPO ₄ ) ₂ .nH ₂ O, Zr (HSO _{3) 2, Zr (HSO 3} ) 2 · nH 2 O, Zr (O 3 P-R 1 -SO 3 H) 2, Zr (O 3 P-R 1 -SO 3 H) 2 · nH 2 O, Zr (O ₃ P—R ² —SO ₃ H) _2-x (O ₃ P—R ³ —COOH) _x , and Zr (O ₃ P—R ² —SO ₃ H) _2−x (O ₃ P—R) ³ _-COOH) in x · _nH 2 O ^(wherein, R 1, ^{R 2,} and ^{R 3} each independently claim 1 is at least one selected from the group consisting of a divalent aromatic group) Or the material of 2. The proton conductive inorganic nanoparticles are titanium compounds, and the titanium compounds include TiO ₂ , TiO ₂ .nH ₂ O, Ti (HPO ₄ ) ₂ , Ti (HPO ₄ ) ₂ .nH ₂ O, Ti (HSO The material according to claim 1 or 2, which is at least one selected from the group consisting of ₃ ) ₂ and Ti (HSO ₃ ) ₂ · nH ₂ O. The material according to claim 1, wherein the proton-conductive inorganic nanoparticles have a Stokes particle size of 20 nm or less by a dynamic light scattering method. The material according to any one of claims 1 to 5, wherein the proton-conductive inorganic nanoparticles have a proton conductivity on the order of 1 x ^10-5 S / cm at a temperature of 20 to 150C. The material according to any one of claims 1 to 6, wherein the proton conductive polymer is one or more of a group of hydrocarbon-based polymers that can be dissolved in a polar organic solvent. 8. The material according to claim 7, wherein the polar organic solvent is selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide. The material according to any one of claims 1 to 8, wherein the proton conductive polymer is one or more of a sulfonated hydrocarbon polymer group. The material according to claim 1, wherein the proton conductive polymer is chemically bonded to the proton conductive inorganic nanoparticles. The material according to any one of claims 1 to 10, wherein the proton-conductive hybrid material is 10 ^-3 S / cm to 1 S / cm at a temperature of -20 to 150 ° C under low and high humidity. A dispersion having a proton conductive hybrid material and a polar organic solvent, wherein the proton conductive hybrid material is selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide. Uniformly dispersed in a polar organic solvent, the proton conducting hybrid material has proton conducting inorganic nanoparticles and a proton conducting polymer, and the Stokes particle size of the proton conducting hybrid material is determined by a dynamic light scattering method. The dispersion described above, which is 20 nm or less. The proton conductive inorganic nanoparticles are at least one selected from the group consisting of zirconium compounds, titanium compounds, cerium compounds, uranium compounds, tin compounds, vanadium compounds, antimony compounds, and calcium hydroxyapatite and hydrated calcium hydroxyapatite. The dispersion according to claim 12 which is a seed. The proton conductive inorganic nanoparticles are zirconium compounds, which are ZrO ₂ , ZrO ₂ .nH ₂ O, Zr (HPO ₄ ) ₂ , Zr (HPO ₄ ) ₂ .nH ₂ O, Zr (HSO _{3) 2, Zr (HSO 3} ) 2 · nH 2 O, Zr (O 3 P-R 1 -SO 3 H) 2, Zr (O 3 P-R 1 -SO 3 H) 2 · nH 2 O, Zr (O ₃ P—R ² —SO ₃ H) _2-x (O ₃ P—R ³ —COOH) _x and Zr (O ₃ P—R ² —SO ₃ H) _2−x (O ₃ P—R) ³ _-COOH) in x · _nH 2 O ^(wherein, R 1, ^{R 2,} and ^{R 3} each independently claim 12 is at least one selected from the group consisting of a divalent aromatic group) Or the dispersion according to 13. The proton conductive inorganic nanoparticles are titanium compounds, and the titanium compounds include TiO ₂ , TiO ₂ .nH ₂ O, Ti (HPO ₄ ) ₂ , Ti (HPO ₄ ) ₂ .nH ₂ O, Ti (HSO The dispersion according to claim 12 or 13, which is at least one selected from the group consisting of ₃ ) ₂ and Ti (HSO ₃ ) ₂ · nH ₂ O. The dispersion according to any one of claims 12 to 15, wherein the proton-conductive inorganic nanoparticles have a Stokes particle size of 20 nm or less by a dynamic light scattering method. The dispersion according to any one of claims 12 to 16, wherein the proton-conductive inorganic nanoparticles have a proton conductivity on the order of 1 x ^10-5 S / cm at a temperature of 20 to 150C. The dispersion according to any one of claims 12 to 17, wherein the proton conductive polymer is one or more of a hydrocarbon-based polymer group that can be dissolved in the polar organic solvent. The dispersion according to any one of claims 12 to 18, wherein the polar organic solvent is selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide and 1-methylpyrrolidone. The dispersion according to any one of claims 12 to 19, wherein the proton conductive polymer is one or more of a sulfonated hydrocarbon polymer group. The dispersion according to any one of claims 12 to 20, wherein the proton conductive polymer is chemically bonded to the proton conductive inorganic nanoparticles. A method for producing a dispersion having a proton conductive hybrid material and a polar organic solvent, the method comprising:
Dissolving a proton conductive polymer in a first polar organic solvent selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide to obtain a polymer solution;
Proton conductivity to a second polar organic solvent selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide which is the same as or different from the first polar organic solvent Dispersing inorganic nanoparticles to obtain a nanoparticle dispersion; and pouring the polymer solution into the nanoparticle dispersion, or pouring the nanoparticle dispersion into the polymer solution, and the organic solvent and proton conductivity. Obtaining the dispersion with a hybrid material,
The method as described above, wherein the material has the proton conductive inorganic nanoparticles and the proton conductive polymer, and the Stokes particle size of the proton conductive hybrid material by a dynamic light scattering method is 20 nm or less. 23. The method of claim 22, further comprising adding a poor organic solvent for the proton conducting polymer to the resulting dispersion to obtain a dispersion having a proton conducting hybrid material having a smaller Stokes particle size. 24. The method of claim 23, wherein the poor organic solvent is selected from the group consisting of methanol, ethanol, isopropanol, butanol and hexane. The proton conductive inorganic nanoparticles are at least one selected from the group consisting of zirconium compounds, titanium compounds, cerium compounds, uranium compounds, tin compounds, vanadium compounds, antimony compounds, and calcium hydroxyapatite and hydrated calcium hydroxyapatite. 25. A method according to any one of claims 22 to 24 which is a seed. The proton conductive inorganic nanoparticles are zirconium compounds, which are ZrO ₂ , ZrO ₂ .nH ₂ O, Zr (HPO ₄ ) ₂ , Zr (HPO ₄ ) ₂ .nH ₂ O, Zr (HSO _{3) 2, Zr (HSO 3} ) 2 · nH 2 O, Zr (O 3 P-R 1 -SO 3 H) 2, Zr (O 3 P-R 1 -SO 3 H) 2 · nH 2 O, Zr (O ₃ P—R ² —SO ₃ H) _2-x (O ₃ P—R ³ —COOH) _x and Zr (O ₃ P—R ² —SO ₃ H) _2−x (O ₃ P—R) ³ _-COOH) in x · _nH 2 O ^(wherein, R 1, ^{R 2,} and ^{R 3} are each independently at least one kind of claim selected from the group consisting of a divalent aromatic group) 22 The method of any one of -25. The proton conductive inorganic nanoparticles are titanium compounds, and the titanium compounds include TiO ₂ , TiO ₂ .nH ₂ O, Ti (HPO ₄ ) ₂ , Ti (HPO ₄ ) ₂ .nH ₂ O, Ti (HSO _3). ) _2, and Ti _{(HSO 3)} the method of any one of claims 22 to 25 is at least one selected from the group consisting of 2 · nH ₂ O. The method according to any one of claims 22 to 27, wherein the proton-conductive inorganic nanoparticles have a Stokes particle size of 20 nm or less by a dynamic light scattering method. The method according to any one of claims 22 to 28, wherein the proton-conductive inorganic nanoparticles have a proton conductivity on the order of 1 x ^10-5 S / cm at a temperature of 20 to 150C. 30. A method according to any one of claims 22 to 29, wherein the proton conducting polymer is one or more of a group of hydrocarbon-based polymers that can be dissolved in the polar organic solvent. 31. The method according to any one of claims 22 to 30, wherein the first and / or second polar organic solvent is selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide and 1-methylpyrrolidone. 32. A method according to any one of claims 22 to 31, wherein the proton conducting polymer is one or more of a sulfonated hydrocarbon-based polymer group. In the step of pouring the polymer solution into the nanoparticle dispersion or the step of pouring the nanoparticle dispersion into the polymer solution, the proton conductive polymer reacts with the proton conductive inorganic nanoparticles, and part or all of the proton conductive polymer 33. The method according to any one of claims 22 to 32, wherein one end of said is chemically bonded to said proton conducting inorganic nanoparticles. A method for producing a proton conducting hybrid material having a proton conducting polymer and proton conducting inorganic nanoparticles, the method comprising:
Dissolving a proton conductive polymer in a first polar organic solvent selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide to obtain a polymer solution;
Proton conductivity in a second polar organic solvent selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide which is the same as or different from the first polar organic solvent Dispersing inorganic nanoparticles to obtain a nanoparticle dispersion; and pouring the polymer solution into the nanoparticle dispersion, or pouring the nanoparticle dispersion into the polymer solution, and the organic solvent and proton conductivity. Obtaining the dispersion having a hybrid material; and removing the first and second polar organic solvents from the obtained dispersion to obtain the proton conductive hybrid material;
The method as described above, wherein the proton conductive hybrid material has a Stokes particle size of 20 nm or less by a dynamic light scattering method. 35. The method of claim 34, further comprising the step of obtaining a dispersion having a proton-conductive hybrid material having a smaller Stokes particle size in addition to the resulting dispersion of a poor organic solvent for the proton-conductive polymer. 36. The method of claim 35, wherein the poor organic solvent is selected from the group consisting of methanol, ethanol, isopropanol, butanol and hexane. The proton conductive inorganic nanoparticles are at least one selected from the group consisting of zirconium compounds, titanium compounds, cerium compounds, uranium compounds, tin compounds, vanadium compounds, antimony compounds, and calcium hydroxyapatite and hydrated calcium hydroxyapatite. 37. A method according to any one of claims 34 to 36 which is a seed. The proton conductive inorganic nanoparticles are zirconium compounds, which are ZrO ₂ , ZrO ₂ .nH ₂ O, Zr (HPO ₄ ) ₂ , Zr (HPO ₄ ) ₂ .nH ₂ O, Zr (HSO ₃ ) ₂ , Zr (HSO ₃ ) ₂ .nH ₂ O, Zr (O ₃ P—R ¹ —SO ₃ H) ₂ , Zr (O ₃ P—R ¹ —SO ₃ H) ₂ .nH ₂ O, Zr ( O ₃ P—R ² —SO ₃ H) _2-x (O ₃ P—R ³ —COOH) _x , and Zr (O ₃ P—R ² —SO ₃ H) _2-x (O ₃ P—R ³ _-COOH) x · _nH 2 O ^(wherein, R 1, ^{R 2,} and ^{R 3} are each independently at least one kind of claim 34 to be selected from the group consisting of a divalent aromatic group) 38. The method according to any one of 37. The proton conductive inorganic nanoparticles are titanium compounds, and the titanium compounds include TiO ₂ , TiO ₂ .nH ₂ O, Ti (HPO ₄ ) ₂ , Ti (HPO ₄ ) ₂ .nH ₂ O, Ti (HSO _3). ) _2, and Ti _{(HSO 3)} the method of any one of claims 34 to 37 is at least one selected from the group consisting of 2 · nH ₂ O. 40. The method according to any one of claims 34 to 39, wherein the proton-conductive inorganic nanoparticles have a Stokes particle size of 20 nm or less by a dynamic light scattering method. 41. The method according to any one of claims 34 to 40, wherein the proton conductive inorganic nanoparticles have a proton conductivity on the order of 1 x ^10-5 S / cm at a temperature of 20 to 150C. 42. A method according to any one of claims 34 to 41, wherein the proton conducting polymer is one or more of a group of hydrocarbon-based polymers that can be dissolved in the polar organic solvent. 43. The method according to any one of claims 34 to 42, wherein the first and / or second polar organic solvent is selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide and 1-methylpyrrolidone. 44. A method according to any one of claims 34 to 43, wherein the proton conducting polymer is one or more of a group of sulfonated hydrocarbon-based polymers. In the step of pouring the polymer solution into the nanoparticle dispersion or the step of pouring the nanoparticle dispersion into the polymer solution, the proton conductive polymer reacts with the proton conductive inorganic nanoparticles, and part or all of the proton conductive polymer 45. The method according to any one of claims 34 to 44, wherein one end of said is chemically bonded to said proton conductive inorganic nanoparticles. A catalyst layer for a fuel cell comprising an electron conductor, a catalyst, and a proton conductive hybrid material,
The proton conductive hybrid material has proton conductive inorganic nanoparticles and a proton conductive polymer;
The catalyst layer, wherein the proton conductive hybrid material has a Stokes particle size of 20 nm or less by a dynamic light scattering method. The said catalyst layer is comprised so that the said catalyst may be carry | supported on the surface of the said electronic conductor, and the said proton conductive hybrid material is arrange | positioned in the vicinity of the position where the said catalyst is arrange | positioned. Catalyst layer. 48. The catalyst layer according to claim 46 or 47, wherein the proton-conductive hybrid material is physically and / or chemically bonded to the electron conductor. The catalyst layer according to any one of claims 46 to 48, wherein the electron conductor is a carbon-based porous electron conductor or a metal-based porous electron conductor. The electron conductor is a carbon-based porous electron conductor, and the carbon-based porous electron conductor is selected from the group consisting of carbon black, acetylene black, graphite, carbon fiber, carbon nanotube, fullerene, activated carbon, and glass carbon. The catalyst layer according to any one of claims 46 to 49, which is selected. The catalyst layer according to any one of claims 46 to 50, wherein the electron conductor has a particle size of 300 nm or less. 52. The catalyst layer according to any one of claims 46 to 51, wherein the catalyst is selected from the group consisting of a noble metal catalyst group and an organic catalyst group. The catalyst layer according to any one of claims 46 to 52, wherein the catalyst has a particle size of 30 nm or less. The proton conductive inorganic nanoparticles are at least one selected from the group consisting of zirconium compounds, titanium compounds, cerium compounds, uranium compounds, tin compounds, vanadium compounds, antimony compounds, and calcium hydroxyapatite and hydrated calcium hydroxyapatite. The catalyst layer according to any one of claims 46 to 53, which is a seed. The proton conductive inorganic nanoparticles are zirconium compounds, and the zirconium compounds include ZrO ₂ , ZrO ₂ .nH ₂ O, Zr (HPO ₄ ) ₂ , Zr (HPO ₄ ) ₂ .nH ₂ O, Zr (HSO ₃ ) ₂ , Zr (HSO ₃ ) ₂ .nH ₂ O, Zr (O ₃ P—R ¹ —SO ₃ H) ₂ , Zr (O ₃ P—R ¹ —SO ₃ H) ₂ .nH ₂ O, Zr ( O ₃ P—R ² —SO ₃ H) _2-x (O ₃ P—R ³ —COOH) _x , and Zr (O ₃ P—R ² —SO ₃ H) _2-x (O ₃ P—R ³ _-COOH) x · _nH 2 O ^(wherein, R 1, ^{R 2,} and ^{R 3} are each independently at least one kind of claim 46 to be selected from the group consisting of a divalent aromatic group) 54. The catalyst layer according to any one of 54. The proton conductive inorganic nanoparticles are titanium compounds, and the titanium compounds include TiO ₂ , TiO ₂ .nH ₂ O, Ti (HPO ₄ ) ₂ , Ti (HPO ₄ ) ₂ .nH ₂ O, Ti (HSO _3). ) _2, and Ti _{(HSO 3)} at least one kind is selected from the group consisting of 2 · nH ₂ O catalyst layer of any one of claims 46-54. 57. The catalyst layer according to any one of claims 46 to 56, wherein the proton conductive inorganic nanoparticles have a Stokes particle size of 20 nm or less by a dynamic light scattering method. 58. The catalyst layer according to any one of claims 46 to 57, wherein the proton conductive inorganic nanoparticles have a proton conductivity on the order of 1 × 10 ⁻⁵ S / cm at a temperature of 20 to 150 ° C. 59. The catalyst layer according to any one of claims 46 to 58, wherein the proton conductive polymer is one or more of a hydrocarbon-based polymer group that can be dissolved in a polar organic solvent. 60. The catalyst layer according to claim 59, wherein the polar organic solvent is selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide. The catalyst layer according to any one of claims 46 to 60, wherein the proton conductive polymer is one or more of a sulfonated hydrocarbon-based polymer group. The catalyst layer according to any one of claims 46 to 61, wherein the proton conductive polymer is chemically bonded to the proton conductive inorganic nanoparticles. A method for producing a fuel cell catalyst layer comprising an electron conductor, a catalyst, and a proton conductive hybrid material, the method comprising:
a) supporting the catalyst on the electron conductor;
b) preparing a proton conductive hybrid material dispersion in which the proton conductive hybrid material is dispersed in a polar organic solvent;
c) mixing the dispersion with the electronic conductor carrying the catalyst to obtain a mixture; and d) applying the mixture to a fuel cell diffusion layer to obtain a fuel cell catalyst layer. Having
The proton conductive hybrid material has proton conductive inorganic nanoparticles and a proton conductive polymer;
The method as described above, wherein the proton conductive hybrid material has a Stokes particle size of 20 nm or less by a dynamic light scattering method. 64. The method of claim 63, further comprising the step of mixing a binder with the mixture during step c) or after step c) and before step d). The method according to claim 63 or 64, further comprising the step of adjusting the viscosity of the mixture by removing a solvent in the mixture. In the step b), the proton conductive polymer is dissolved in a first polar organic solvent selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide to obtain a polymer solution. Process;
Proton conductivity in a second polar organic solvent selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide which is the same as or different from the first polar organic solvent 64. The method further comprising: dispersing inorganic nanoparticles to obtain a nanoparticle dispersion; and pouring the polymer solution into the nanoparticle dispersion or pouring the nanoparticle dispersion into the polymer solution. 66. The method according to any one of 65. 67. The step b) further comprises a step of obtaining a dispersion having a proton conductive hybrid material having a smaller Stokes particle size in addition to the obtained dispersion of a poor organic solvent for the proton conductive polymer. the method of. 68. The method of claim 67, wherein the poor organic solvent is selected from the group consisting of methanol, ethanol, isopropanol, butanol and hexane. In the step b), the proton conductive polymer reacts with the proton conductive inorganic nanoparticles, and a part or all of one end of the proton conductive polymer is chemically bonded to the proton conductive inorganic nanoparticles. Item 69. The method according to any one of Items 63 to 68. The said catalyst layer is comprised so that the said catalyst may be carry | supported on the surface of the said electronic conductor, and the said proton conductive hybrid material is arrange | positioned in the vicinity of the position where the said catalyst is arrange | positioned. 70. The method according to any one of 69. 71. A method according to any one of claims 63 to 70, wherein the proton conducting hybrid material is physically and / or chemically bonded to the electronic conductor. The method according to any one of claims 63 to 71, wherein the electron conductor is a carbon-based porous electron conductor or a metal-based porous electron conductor. The electron conductor is a carbon-based porous electron conductor, and the carbon-based porous electron conductor is selected from the group consisting of carbon black, acetylene black, graphite, carbon fiber, carbon nanotube, fullerene, activated carbon, and glass carbon. 73. The method according to any one of claims 63 to 72, which is selected. 74. The method according to any one of claims 63 to 73, wherein the electron conductor has a particle size of 300 nm or less. The method according to any one of claims 63 to 74, wherein the catalyst is selected from the group consisting of a noble metal catalyst group and an organic catalyst group. The method according to any one of claims 63 to 75, wherein the catalyst has a particle size of 30 nm or less. The proton conductive inorganic nanoparticles are at least one selected from the group consisting of zirconium compounds, titanium compounds, cerium compounds, uranium compounds, tin compounds, vanadium compounds, antimony compounds, and calcium hydroxyapatite and hydrated calcium hydroxyapatite. 77. A method according to any one of claims 63 to 76. The proton conductive inorganic nanoparticles are zirconium compounds, which are ZrO ₂ , ZrO ₂ .nH ₂ O, Zr (HPO ₄ ) ₂ , Zr (HPO ₄ ) ₂ .nH ₂ O, Zr (HSO ₃ ). ₂ , Zr (HSO ₃ ) ₂ .nH ₂ O, Zr (O ₃ P—R ¹ —SO ₃ H) ₂ , Zr (O ₃ P—R ¹ —SO ₃ H) ₂ .nH ₂ O, Zr (O ^{_{3 P-R 2 -SO 3 H}} ) 2-x (O 3 P-R 3 -COOH) x, and ^{_{Zr (O 3 P-R 2}} -SO 3 H) 2-x (O 3 P-R 3 - COOH) _x · nH ₂ O (wherein R ¹ , R ² , and R ³ each independently represents a divalent aromatic group), and is at least one selected from the group consisting of: The method of any one of these. Proton conductive inorganic nanoparticles are titanium compounds, which are TiO ₂ , TiO ₂ .nH ₂ O, Ti (HPO ₄ ) ₂ , Ti (HPO ₄ ) ₂ .nH ₂ O, Ti (HSO ₃ ). _2, and Ti _{(HSO 3)} the method of any one of claims 63 to 77 is at least one selected from the group consisting of 2 · nH ₂ O. The method according to any one of claims 63 to 79, wherein the proton-conductive inorganic nanoparticles have a Stokes particle size of 20 nm or less by a dynamic light scattering method. The method according to any one of claims 63 to 80, wherein the proton-conductive inorganic nanoparticles have a proton conductivity of the order of 1 x ^10-5 S / cm at a temperature of 20 to 150C. 82. A method according to any one of claims 63 to 81, wherein the proton conducting polymer is one or more of a group of hydrocarbon-based polymers that can be dissolved in a polar organic solvent. 83. The method according to any one of claims 66 to 82, wherein the polar organic solvent is selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide. 84. A method according to any one of claims 63 to 83, wherein the proton conducting polymer is one or more of a group of sulfonated hydrocarbon-based polymers. An electrolyte membrane for a fuel cell having a proton conductive hybrid material, the proton conductive hybrid material having proton conductive inorganic nanoparticles and a proton conductive polymer, and dynamic light scattering of the proton conductive hybrid material Said electrolyte membrane whose Stokes particle size by a method is 20 nm or less. 86. The electrolyte membrane according to claim 85, wherein the electrolyte membrane has a substrate, and the proton conductive hybrid material is chemically and / or physically bonded to the substrate. 90. The electrolyte membrane according to claim 86, wherein the substrate is selected from the group consisting of a porous polymer and a porous ceramic. The proton conductive inorganic nanoparticles are at least one selected from the group consisting of zirconium compounds, titanium compounds, cerium compounds, uranium compounds, tin compounds, vanadium compounds, antimony compounds, and calcium hydroxyapatite and hydrated calcium hydroxyapatite. The electrolyte membrane according to any one of claims 85 to 87. The proton conductive inorganic nanoparticles are zirconium compounds, which are ZrO ₂ , ZrO ₂ .nH ₂ O, Zr (HPO ₄ ) ₂ , Zr (HPO ₄ ) ₂ .nH ₂ O, Zr (HSO ₃ ). ₂ , Zr (HSO ₃ ) ₂ .nH ₂ O, Zr (O ₃ P—R ¹ —SO ₃ H) ₂ , Zr (O ₃ P—R ¹ —SO ₃ H) ₂ .nH ₂ O, Zr (O ^{_{3 P-R 2 -SO 3 H}} ) 2-x (O 3 P-R 3 -COOH) x, and ^{_{Zr (O 3 P-R 2}} -SO 3 H) 2-x (O 3 P-R 3 - COOH) _x · nH ₂ O (wherein R ¹ , R ² , and R ³ each independently represents a divalent aromatic group), and is at least one selected from the group consisting of 85 to 88. The electrolyte membrane according to any one of the above. Proton conductive inorganic nanoparticles are titanium compounds, which are TiO ₂ , TiO ₂ .nH ₂ O, Ti (HPO ₄ ) ₂ , Ti (HPO ₄ ) ₂ .nH ₂ O, Ti (HSO ₃ ). _2, and _{Ti (HSO 3) 2 · nH} 2 at least one kind of any one electrolyte membrane according to claim 85 to 87 in which O is selected from the group consisting of. The electrolyte membrane according to any one of claims 85 to 90, wherein the proton-conductive inorganic nanoparticles have a Stokes particle size of 20 nm or less by a dynamic light scattering method. 92. The electrolyte membrane according to any one of claims 85 to 91, wherein the proton conductive inorganic nanoparticles have a proton conductivity on the order of 1 × 10 ⁻⁵ S / cm at a temperature of 20 to 150 ° C. The electrolyte membrane according to any one of claims 85 to 92, wherein the proton conductive polymer is one or more of a hydrocarbon-based polymer group that can be dissolved in a polar organic solvent. 94. The electrolyte membrane according to claim 93, wherein the polar organic solvent is selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide. 95. The electrolyte membrane according to any one of claims 85 to 94, wherein the proton conductive polymer is one or more of a sulfonated hydrocarbon polymer group. 96. The electrolyte membrane according to any one of claims 85 to 95, wherein the proton conductive polymer is chemically bonded to the proton conductive inorganic nanoparticles. The electrolyte membrane according to any one of claims 85 to 96, wherein the electrolyte membrane for a fuel cell is 10 ^-2 S / cm to 5 S / cm at a temperature of -20 to 150 ° C under low and high humidity. A method for producing an electrolyte membrane for a fuel cell having a porous substrate and a proton conductive hybrid material, the method comprising:
x) preparing a proton conductive hybrid material dispersion in which the proton conductive hybrid material is dispersed in a polar organic solvent; and y) applying the dispersion to the holes of the substrate or the holes and surface of the substrate. And obtaining a fuel cell electrolyte membrane,
The proton conductive hybrid material has proton conductive inorganic nanoparticles and a proton conductive polymer;
The method as described above, wherein the proton conductive hybrid material has a Stokes particle size of 20 nm or less by a dynamic light scattering method. Said step x)
Dissolving the proton conductive polymer in a first polar organic solvent selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide to obtain a polymer solution;
Proton conductivity to a second polar organic solvent selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide which is the same as or different from the first polar organic solvent 99. The method further comprising: dispersing inorganic nanoparticles to obtain a nanoparticle dispersion; and pouring the polymer solution into the nanoparticle dispersion or pouring the nanoparticle dispersion into the polymer solution. the method of. 99. The step b) further comprises adding a poor organic solvent for the proton conducting polymer to the resulting dispersion to obtain a dispersion having a proton conducting hybrid material with a smaller Stokes particle size. The method described. 101. The method of claim 100, wherein the poor organic solvent is selected from the group consisting of methanol, ethanol, isopropanol, butanol and hexane. In the step x), the proton conductive polymer reacts with the proton conductive inorganic nanoparticles, and a part or all of one end of the proton conductive polymer is chemically bonded to the proton conductive inorganic nanoparticles. Item 101. The method according to any one of Items 98 to 101. 99. In the step y), the proton conductive polymer reacts with pores and / or surfaces of the substrate, and a part or all of one end of the proton conductive polymer is chemically bonded to the substrate. 102. The method of any one of -102. 104. The method according to any one of claims 98 to 103, wherein the substrate is selected from the group consisting of a porous polymer and a porous ceramic. The proton conductive inorganic nanoparticles are at least one selected from the group consisting of zirconium compounds, titanium compounds, cerium compounds, uranium compounds, tin compounds, vanadium compounds, antimony compounds, and calcium hydroxyapatite and hydrated calcium hydroxyapatite. 105. A method according to any one of claims 98 to 104. The proton conductive inorganic nanoparticles are zirconium compounds, which are ZrO ₂ , ZrO ₂ .nH ₂ O, Zr (HPO ₄ ) ₂ , Zr (HPO ₄ ) ₂ .nH ₂ O, Zr (HSO ₃ ). ₂ , Zr (HSO ₃ ) ₂ .nH ₂ O, Zr (O ₃ P—R ¹ —SO ₃ H) ₂ , Zr (O ₃ P—R ¹ —SO ₃ H) ₂ .nH ₂ O, Zr (O ^{_{3 P-R 2 -SO 3 H}} ) 2-x (O 3 P-R 3 -COOH) x, and ^{_{Zr (O 3 P-R 2}} -SO 3 H) 2-x (O 3 P-R 3 - COOH) _x · nH ₂ O (wherein R ¹ , R ² , and R ³ each independently represents a divalent aromatic group) is at least one selected from the group consisting of claims 98 to 105 The method of any one of these. Proton conductive inorganic nanoparticles are titanium compounds, which are TiO ₂ , TiO ₂ .nH ₂ O, Ti (HPO ₄ ) ₂ , Ti (HPO ₄ ) ₂ .nH ₂ O, Ti (HSO ₃ ). _2, and Ti _{(HSO 3)} the method of any one of claims 98 to 105 is at least one selected from the group consisting of 2 · nH ₂ O. 108. The method according to any one of claims 98 to 107, wherein the proton-conductive inorganic nanoparticles have a Stokes particle size of 20 nm or less by a dynamic light scattering method. 109. The method according to any one of claims 98 to 108, wherein the proton conductive inorganic nanoparticles have a proton conductivity on the order of 1 * 10 < ^-5 > S / cm at a temperature of 20 to 150 <0> C. 110. A method according to any one of claims 98 to 109, wherein the proton conducting polymer is one or more of a group of hydrocarbon-based polymers that can be dissolved in a polar organic solvent. 111. The method according to any one of claims 99 to 110, wherein the polar organic solvent is selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide and 1-methylpyrrolidone. 112. A method according to any one of claims 98 to 111, wherein the proton conducting polymer is one or more of a group of sulfonated hydrocarbon-based polymers. Proton-conducting inorganic nanoparticles or a dispersion comprising the proton-conducting inorganic nanoparticle precursor and a polar organic solvent, wherein the proton-conducting inorganic nanoparticles or precursor thereof are uniformly dispersed in the polar organic solvent. In addition, the proton conductive inorganic nanoparticle or a precursor thereof is the above dispersion, wherein the Stokes particle size by a dynamic light scattering method is 20 nm or less. 114. The dispersion of claim 113, wherein the polar organic solvent is selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide. The proton conductive inorganic nanoparticles or precursors thereof are selected from the group consisting of zirconium compounds, titanium compounds, cerium compounds, uranium compounds, tin compounds, vanadium compounds, antimony compounds, and calcium hydroxyapatite and hydrated calcium hydroxyapatite. The dispersion according to claim 113 or 114, which is at least one selected from the group consisting of: The proton conductive inorganic nanoparticles or precursors thereof are zirconium compounds, which are ZrO ₂ , ZrO ₂ .nH ₂ O, Zr (HPO ₄ ) ₂ , Zr (HPO ₄ ) ₂ .nH ₂ O, Zr. (HSO ₃ ) ₂ , Zr (HSO ₃ ) ₂ .nH ₂ O, Zr (O ₃ P—R ¹ —SO ₃ H) ₂ , Zr (O ₃ P—R ¹ —SO ₃ H) ₂ .nH ₂ O , Zr (O ₃ P—R ² —SO ₃ H) _2-x (O ₃ P—R ³ —COOH) _x , and Zr (O ₃ P—R ² —SO ₃ H) _2-x (O ₃ P —R ³ —COOH) _x · nH ₂ O (wherein R ¹ , R ² , and R ³ each independently represents a divalent aromatic group) is at least one selected from the group consisting of 120. The dispersion according to any one of Items 113 to 115. The proton conductive inorganic nanoparticles or precursors thereof are titanium compounds, and the titanium compounds include TiO ₂ , TiO ₂ .nH ₂ O, Ti (HPO ₄ ) ₂ , Ti (HPO ₄ ) ₂ .nH ₂ O, Ti. _{(HSO 3) 2,} and Ti _{(HSO 3)} is at least one selected from the group consisting of 2 · nH ₂ O dispersion described in any one of claims 113-115. 118. The dispersion according to any one of claims 113 to 117, wherein the proton-conductive inorganic nanoparticles have a proton conductivity on the order of 1 × 10 ⁻⁵ S / cm at a temperature of 20 to 150 ° C. A method for producing a dispersion having proton conductive inorganic nanoparticles or a proton conductive inorganic nanoparticle precursor and a polar organic solvent, the method comprising:
i) preparing proton conductive inorganic nanoparticles or precursors thereof; and
ii) having the step of uniformly dispersing the proton conductive nano-inorganic particles or precursors thereof in the polar organic solvent,
The above method, wherein the proton-conductive inorganic nanoparticles or precursors thereof have a Stokes particle size of 20 nm or less by a dynamic light scattering method. The step of preparing the proton conductive nano inorganic particles or precursors thereof,
Preparing a solution of an organic solvent of a metal alkoxide (where the metal is selected from the group consisting of zirconium, titanium, cerium, uranium, tin, vanadium, arsenic, and calcium); and hydrolyzing the solution to provide the proton conductivity 120. The method of claim 119, further comprising the step of obtaining nano-inorganic particles or a precursor thereof. 121. The method according to claim 119 or 120, wherein the polar organic solvent is selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide. The proton conductive inorganic nanoparticles or precursors thereof are selected from the group consisting of zirconium compounds, titanium compounds, cerium compounds, uranium compounds, tin compounds, vanadium compounds, antimony compounds, and calcium hydroxyapatite and hydrated calcium hydroxyapatite. 122. The method according to any one of claims 119 to 121, wherein the method is at least one selected from the group consisting of: The proton conductive inorganic nanoparticles or precursors thereof are zirconium compounds, which are ZrO ₂ , ZrO ₂ .nH ₂ O, Zr (HPO ₄ ) ₂ , Zr (HPO ₄ ) ₂ .nH ₂ O, Zr. (HSO ₃ ) ₂ , Zr (HSO ₃ ) ₂ .nH ₂ O, Zr (O ₃ P—R ¹ —SO ₃ H) ₂ , Zr (O ₃ P—R ¹ —SO ₃ H) ₂ .nH ₂ O , Zr (O ₃ P—R ² —SO ₃ H) _2-x (O ₃ P—R ³ —COOH) _x , and Zr (O ₃ P—R ² —SO ₃ H) _2-x (O ₃ P —R ³ —COOH) _x · nH ₂ O (wherein R ¹ , R ² , and R ³ each independently represents a divalent aromatic group) is at least one selected from the group consisting of 122. The method according to any one of items 119 to 122. The proton conductive inorganic nanoparticles or precursors thereof are titanium compounds, and the titanium compounds include TiO ₂ , TiO ₂ .nH ₂ O, Ti (HPO ₄ ) ₂ , Ti (HPO ₄ ) ₂ .nH ₂ O, Ti. The method according to any one of claims 119 to 122, wherein the method is at least one selected from the group consisting of (HSO ₃ ) ₂ and Ti (HSO ₃ ) ₂ · nH ₂ O. 125. The method according to any one of claims 119 to 124, wherein the proton-conductive inorganic nanoparticles have a proton conductivity on the order of 1 x ^10-5 S / cm at a temperature of 20 to 150C. A proton conductive hybrid material having a proton conductive inorganic mesoporous material and a proton conductive polymer, wherein the proton conductive inorganic mesoporous material has a pore diameter of 20 nm or less. Proton conductive inorganic mesoporous materials include mesoporous zirconium compounds, mesoporous titanium compounds, mesoporous cerium compounds, mesoporous uranium compounds, mesoporous tin compounds, mesoporous vanadium compounds, mesoporous antimony compounds, and mesoporous calcium hydroxyapatite and mesoporous hydrated calcium hydroxyapatite. 127. The material according to claim 126, wherein the material is at least one selected from the group consisting of: The proton conductive inorganic mesoporous material is a mesoporous zirconium compound, and the mesoporous zirconium compound includes mesoporous ZrO ₂ , mesoporous ZrO ₂ · nH ₂ O, mesoporous Zr (HPO ₄ ) ₂ , and mesoporous Zr (HPO ₄ ) ₂ · nH ₂ O. , Mesoporous Zr (HSO ₃ ) ₂ , mesoporous Zr (HSO ₃ ) ₂ .nH ₂ O, mesoporous Zr (O ₃ P—R ¹ —SO ₃ H) ₂ , mesoporous Zr (O ₃ P—R ¹ —SO ₃ H) ) ₂ · nH ₂ O, mesoporous Zr (O ₃ P—R ² —SO ₃ H) _2−x (O ₃ P—R ³ —COOH) _x , and mesoporous Zr (O ₃ P—R ² —SO ₃ H) ) each ^{_{2-x (O 3 P-}} R 3 -COOH) x · nH 2 O ( ^wherein, R 1, ^{R 2,} and ^{R 3} The standing, the material according to claim 126 or 127, wherein at least one selected from the group consisting of a divalent aromatic group). The proton conductive inorganic mesoporous material is a mesoporous titanium compound, and the mesoporous titanium compound includes mesoporous TiO ₂ , mesoporous TiO ₂ · nH ₂ O, mesoporous Ti (HPO ₄ ) ₂ , and mesoporous Ti (HPO ₄ ) ₂ · nH ₂ O. 128. The material according to claim 126 or 127, which is at least one selected from the group consisting of: mesoporous Ti (HSO ₃ ) ₂ and mesoporous Ti (HSO ₃ ) ₂ .nH ₂ O. 131. The material according to any one of claims 126 to 129, wherein the proton conductive inorganic mesoporous material has a proton conductivity on the order of 1 × 10 ⁻⁵ S / cm at a temperature of 20 to 150 ° C. 131. A material according to any one of claims 126 to 130, wherein the proton conducting polymer is one or more of a group of hydrocarbon-based polymers that can be dissolved in a polar organic solvent. 132. The material of claim 131, wherein the polar organic solvent is selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, 1-methylpyrrolidone and N-methylacetamide. The material according to any one of claims 126 to 132, wherein the proton conducting polymer is one or more of a group of sulfonated hydrocarbon-based polymers. 134. A material according to any one of claims 126 to 133, wherein the proton conducting polymer is chemically bonded to the proton conducting inorganic mesoporous material. 135. The proton conductive hybrid material has proton conductivity of 10 < ^-3 > S / cm to 1 S / cm at a temperature of -20 to 150 [deg.] C. under low and high humidity. Material. A fuel cell comprising the proton-conductive hybrid material according to claim 1. 63. A fuel cell comprising the catalyst layer according to any one of claims 46 to 62. A fuel cell comprising the electrolyte membrane according to any one of claims 85 to 97. A fuel cell comprising the proton conductive hybrid material according to any one of claims 126 to 135. 135. A fuel cell catalyst layer comprising the proton conductive hybrid material according to any one of claims 126 to 135. 141. A fuel cell having the catalyst layer of claim 140. 136. An electrolyte membrane for a fuel cell comprising the proton conductive hybrid material according to any one of claims 126 to 135. 143. A fuel cell comprising the electrolyte membrane according to claim 142.

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